Trends in Analytical Chemistry 85 (2016) 203220

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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

Nanomaterials as sorbents for food sample analysis

Javier Gonzlez-Slamo, Brbara Socas-Rodrguez, Javier Hernndez-Borges *,
Miguel ngel Rodrguez-Delgado
Departamento de Qumica, Unidad Departamental de Qumica Analtica, Facultad de Ciencias, Seccin de Qumica, Universidad de La Laguna (ULL).
Avenida Astrofsico Fco. Snchez, s/n. 38206 San Cristbal de La Laguna, Tenerife, Islas Canarias, Espaa

A R T I C L E I N F O A B S T R A C T

Keywords:
The discovery of nanomaterials has bestowed a great impact in the improvement and development of
Carbon nanotubes
many disciplines, including Analytical Chemistry, as a result of their particular properties that result highly
Coatings
Food
adequate for an extensive variety of applications. Among them, metal-organic frameworks, magnetic and
Graphene non-magnetic nanoparticles, carbon nanotubes and graphene, as well as their combinations, are the most
Metal-organic frameworks important nanomaterials that have been used up to now, especially in sorbent-based extraction tech-
Nanomaterials niques. Many of them have been demonstrated to be highly appropriate for the extraction of a wide variety
Nanoparticles of analytes even from highly complex samples like foods. This review article is aimed at summarizing
Sorbents the most recent applications of such nanomaterials in food analysis. Particular attention has been paid
to provide a general vision of the wide variety of sorbents that are currently being developed in this eld.
2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction ........................................................................................................................................................................................................................................................ 204

2. Metal-organic frameworks ............................................................................................................................................................................................................................ 204
3. Magnetic and non-magnetic nanoparticles ............................................................................................................................................................................................. 206
4. Carbon nanotubes ............................................................................................................................................................................................................................................. 210
5. Graphene .............................................................................................................................................................................................................................................................. 213
6. Combination of different nanomaterials ................................................................................................................................................................................................... 215
7. Conclusions ......................................................................................................................................................................................................................................................... 216
Acknowledgements .......................................................................................................................................................................................................................................... 217
References ............................................................................................................................................................................................................................................................ 217

Abbreviations: dSPE, micro-dispersive solid-phase extraction; 17-E2, 17-estradiol; AAS, atomic absorption spectroscopy; AMT, 2-amino-5-mercapto-1,3,4-
thiadiazole; BMA, butyl methacrylate; BP, buckypaper; BPA, bisphenolA; BSM, methyl -(4,6-dimethoxypryrimidin-2-yl-carbamoyl sulfamoyl)-O-toluate; CAP, chloramphenicol;
CE, capillary electrophoresis; CNTF, carbon nanotube lm; CNTs, carbon nanotubes; DAD, diode array detector; DBP, dibutyl phthalate; DCBI, desorption corona beam ion-
ization; DLLME, dispersive liquid-liquid microextraction; DVB, divinylbenzene; EAAS, electrothermal atomization atomic absorption spectroscopy; ECD, electron capture
detector; ECLIA, electrochemiluminescent immunoassay; EDMA, ethylene dimethacrylate; FAAS, ame atomic absorption spectrometry; FD, uorescence detection; FID, ame
ionisation detector; GC, gas chromatography; GFAAS, graphite furnace atomic absorption spectrometry; GO, graphene oxide; HF, hollow ber; HLB, Hydrophilic-lipophilic
balance copolymer; HPLC, high performance liquid chromatography; HS-SPME, Head-space-SPME; ICP, inductively coupled plasma; IIP, ion imprinted polymer; ILs, ionic
liquids; IS, internal standard; LODs, limits of detection; LPME, liquid-phase microextraction; MALDI, matrix-assisted laser desorption/ionization; m-dSPE, magnetic-
dispersive solid-phase extraction; m-dSPIE, magnetic-dispersive solid-phase immunoextraction; MIL, Materials of Institute Lavoisier; MIP, molecularly imprinted polymer;
MNC, magnetic nanoporous carbon; MOFs, metal-organic frameworks; MPPC, 3-(1-Methyl-1H-pyrrol-2-yl)-1H-pyrazole-5-carboxylic acid; MS, mass spectrometry; MSPD,
matrix solid-phase dispersion; MWCNTs, multi-walled carbon nanotubes; MWCNTs-OH, hydroxyl functionalized multi-walled carbon nanotubes; nano-UHPLC, nano ultra-
high performance liquid chromatography; NPs, nanoparticles; OCPs, organochlorine pesticides; OES, optical emission spectrometry; OMIM, 1-octyl-3-methylimidazole; OPPs,
organophosphorous pesticides; PAMAM, polyamidoamine; PAN, 1-(2-pyridylazo)-2-naphthol; PANI, polyaniline; PAR, 4-(2-pyridylazo) resorcinol; PCBs, polychlorinated bi-
phenyls; PDDA, poly(diallyldimethylammonium chloride); PEA, phenylethyl amine; PIL, polymeric ionic liquid; PNPEA, poly (N-phenylethanolamine); PPy, polypyrrole; PTES,
propyltriethoxysilan; PVA, poly(vinyl alcohol); QDs, quantum dots; SBSE, stir bar sorptive extraction; SDS, sodium dodecyl sulphate; SDZ, sulfadiazine; SMO, sulfamethoxazole;
SPE, solid-phase extraction; SPME, solid-phase microextraction; SWCNTs, single-walled carbon nanotubes; TBBPA, tetrabromobisphenol A; TCA, 2,4,6-trichloroanisole; TMSPT,
3-(trimethoxysilyl)-1-propantiol; TPP, triphenyl phosphate; UFLC, ultra-fast liquid chromatography; US-dSPE, ultrasound assisted-dispersive solid-phase extraction; UV, ul-
traviolet; VA-m-dSPE, vortex assisted-magnetic-dispersive solid-phase extraction; ZIF, zeolitic imidazolate framework.
* Corresponding author. Tel.: + 34 922 31 65 02 (ext. 6946).
E-mail address: jhborges@ull.edu.es (J. Hernndez-Borges).

http://dx.doi.org/10.1016/j.trac.2016.09.009
0165-9936/ 2016 Elsevier B.V. All rights reserved.
204 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
1. Introduction
Nanoscience is currently expanding to diverse areas where its
application is continuously increasing due to the unique optical, elec-
tronic, magnetic, and catalytic characteristics that nanomaterials
present [1]. Particularly in the eld of Analytical Chemistry, the im-
portant advancements achieved in nanomaterial synthesis and
characterization have allowed the development of new analytical
methodologies [2,3], since their specic physical and chemical
properties associated with their nano-size structure also provide
numerous advantages in this eld. In fact, there is a wide variety
of applications which include their use as materials for the con-
struction of electrochemical sensors or biosensors, supports,
and sorbents for the analysis of different groups of analytes in a
wide variety of matrices of environmental, biological and food nature
[4,5].
The application of nanomaterials as sorbents has achieved a sharp
increase in recent years since they can play an important role in
sample and pre-concentration processes. In this sense, their low re-
sistance to diffusion, large adsorptive capability and fast sorption
kinetics are characteristics especially relevant in analyte concen-
tration and interference removal, aspects of vital importance in the
trace analysis of both organic and inorganic species in complex
samples [1,3].
Due to the current globalized food production system, food
safety and quality assessment are paramount concerns of national
and international regulatory committees and, consequently, for
the scientic community [6]. In this sense, numerous improve-
ments have been developed in order to enhance the speed and
reliability of analytical processes. However, food sample analysis
constitutes one of the most important challenges in Analytical
Chemistry due to the high complexity of these matrices which
contain a large number of components with different nature and
chemical properties. These aspects considerably hinder the selec-
tive extraction of the target analytes, that decrease the sensitivity
of the methodology and that, in some cases, could even damage
the separation method and determination systems as occurs
with the presence of salts, lipids or proteins [7]. That is why
the application of effective sample pre-treatment techniques that
provide high extraction eciency and offer an adequate clean-up
of the samples is crucial. In this sense, the development of
nanomaterials as sorbents has become an interesting alternative
for such a purpose.
In this concern, diverse types of nano-sorbents have been
evaluated in food analysis, such as carbon nanotubes (CNTs),
graphene and graphene oxide (GO), nanoparticles (NPs) of
different nature, metal-organic frameworks (MOFs) as well as
diverse combinations of them using the synergy of their
individual characteristics. Regarding their applications, those
have been based on the development of diverse extraction
processes including conventional solid-phase extraction (SPE),
dispersive solid-phase extraction (dSPE) in the same way as its
micro (dSPE) and magnetic (m-dSPE) approaches, solid-phase
microextraction (SPME), matrix solid-phase dispersion (MSPD),
stir bar sorptive extraction (SBSE) or even in hollow ber (HF)
liquid-phase microextraction (LPME) techniques in which the
pores of the bre are lled with such nanomaterials together with
an organic solvent.
The advantages that nanomaterials offer for food analysis have
resulted in a large variety of applications and an important in-
crease in the number of publications focused on their evaluation.
In this article we review the principal nanosorbents used in this
eld, presenting their most relevant characteristics and paying
special attention to the most novel studies and their applications
for the extraction of both organic and inorganic analytes in food
matrices.
2. Metal-organic frameworks
Metal-organic frameworks (MOFs) are an emerging class of
porous materials constituted by the self-assembling of metal cations
and organic electron donors through coordination bonds. The large
variety of metallic ions and organic ligands available and the mul-
tiple ways in which they can be combined, allow obtaining different
pore diameters and modifying the size of the cavities inside the
three-dimensional structure. In fact, it is precisely this capacity to
be modied, in addition to their large surface area, the possible
functionalization of their internal surface as well as their thermal
and chemical stability, which have upgraded the use of MOFs in
diverse applications, attracting a special interest as sorbents in an-
alytical applications.
In spite of their obvious advantages, it is noteworthy to mention
that the application of MOFs as sorbents in food analysis has been
quite limited, as can be deduced from the few papers found in the
literature so far [814].
Attending to the information shown in Table 1, which com-
piles some examples of the application of MOFs for the extraction
of different compounds from food matrices, it seems clear that
one of the sample treatment techniques most commonly used
has been dSPE for both analyte extraction [11,13] and sample
clean-up [10], especially their dSPE approach in which very
low amounts of sorbent are applied. In these papers, the same
MOF [MIL-101(Cr) (Materials of Institute Lavoisier)] was applied
for the extraction of seven herbicides from soybean [10], corn,
soybean, sunower and peanut oil [11], as well as from peanuts
[13].
Some other work has been published using MOFs as MSPD
sorbents [12,14]. In these examples, two slightly different MOFs
were employed. In one of them, [(Nd0.9Eu0.1)2(DPA)3(H2O)3] was
used for the extraction of six pesticides from Annona muricata
samples [12] while for the other, [(La0.9Eu0.1)2(DPA)3(H2O)3]
was applied to extract other six pesticides from lettuce samples
[14].
In most of these applications of MOFs as sorbents, high perfor-
mance liquid chromatography (HPLC) coupled to diode array
detectors (DAD) were employed [1013], though in a few cases either
gas chromatography (GC) with mass spectrometry (MS) detection
[14] or nano ultra-high performance liquid chromatography (nano-
UHPLC) with ultraviolet (UV) detection have also been used [9]. It
is also noteworthy to mention that recovery values between 70 and
120% were obtained in all cases with limits of detection (LODs) in
the order of a few g/L or g/kg independently of the MOF and tech-
nique used.
Besides the above-mentioned uses of MOFs, these nanomaterials
have been applied in some different ways. The work of Lin et al. [8]
is an example of this fact. In this paper, authors used MOF-5 to cover
a stainless steel wire and to use it as a support to immobilize an
aptamer capable of recognizing the target analytes (two polychlo-
rinated biphenyls (PCBs)) on its surface. Thus, they created a highly
selective sorbent to extract the analytes of interest from sh with
a good extraction eciency and low LODs.
Apart from the previous applications, MOFs may also be used
as substrates to create other structures. This is the case of the work
of Liu et al. in which the MOF (ZIF-67 (zeolitic imidazolate frame-
work)) has been used as the base for building a magnetic nanoporous
carbon by the calcination of the MOF three-dimensional structure
[15]. This new sorbent was applied in magnetic dSPE (m-dSPE) for
the extraction of four phenylurea herbicides from grape and bitter
gourd samples, using HPLC-UV for their determination. In this way,
it was possible to obtain recoveries between 89 and 105% with LODs
in the range 0.170.46 g/kg. Up to now, and to the best of our
knowledge, this is the only paper that has been published regard-
ing this issue.
Table 1
Applications of MOFs as sorbents used for the analysis of food matrices

Nanomaterial Sample Determination Analytes Matrix Recovery LODs Comments Reference

treatment technique %

MOF-5@aptamer on stainless SPME GC-MS 2 PCBs Fish 8997 0.150.22 ng/Kg MOF used as substrate to immobilize [8]
steel wire (-) the aptamer
MIL-53(Al)-poly(BMA-EDMA) SPE Nano-UHPLC-UV 6 penicillin antibiotics Milk 81101 0.060.26 g/L [9]

J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220

monolithic column (3 mg)
MIL-101(Cr) (5 mg) dSPE HPLC-DAD 7 herbicides Soybean 91107 1.562.00 g/Kg [10]
MIL-101(Cr) (7 mg) dSPE HPLC-DAD 7 herbicides Soybean, corn, sunower 87107 0.5851.04 g/L Comparison with the QuEChERS [11]
and peanut oil method
MNC(ZIF-67) (10 mg) m-dSPE HPLC-UV 4 phenylurea herbicides Grape, bitter gourd 89105 0.170.46 g/Kg [15]
[(Nd0.9Eu0.1)2(DPA)3(H2O)3] (1 g) MSPD HPLC-DAD 6 pesticides Annona muricata 7888 3050 g/Kg [12]
MIL-101(Cr) (7 mg) dSPE HPLC-DAD 7 herbicides Peanuts 96102 0.981.9 g/Kg [13]
[(La0.9Eu0.1)2(DPA)3(H2O)3] (0.5 g) MSPD GC-MS 6 pesticides Lettuce 78107 2050 g/Kg [14]

Combined with other nanomaterials

MOF-5@IL@Graphene on etched SPME GC-FID Chloramphenicol, Milk, honey 87103 14.819.5 ng/L [16]
stainless steel wire (-) thiamphenicol
Fe3O4@dipyridylamine@MIL-101(Fe) (-) m-dSPE FAAS Cd(II), Pb(II), Co(II), Ni(II) Fish 88108 0.130.75 g/L Method validated using certied [17]
reference materials
Fe3O4@DMcT-MOF (-) dSPE FAAS Cd(II), Pb(II), Zn(II) Baby food 90106 0.100.75 g/L Method validated using certied [18]
reference materials
Fe3O4@MOF-5(Fe) (-) SBSE GC-MS 6 PCBs Snakehead sh, crucian 9397 0.0610.096 g/Kg [19]
carp, grass carp
Fe3O4@MIL-100(Cr) (10 mg) Automatic Spectrophotometric Malachite green Fish 103107 0.012 mg/L [20]
in-Syringe detection
m-dSPE
Fe3O4ethylenediamine/ m-dSPE FAAS Cd(II), Pb(II), Zn(II), Cr(III) Leek, fenugreek, parsley, 87108 0.150.80 g/L Validation using certied reference [21]
MIL-101(Fe) (-) radish, radish leaves, materials
beetroot leaves, garden
cress, basil, coriander
SH-Fe3O4/Cu3(BTC)2 (10 mg) m-dSPE FAAS Pb(II) Rice, pig liver, tea leaves 97104 0.29 g/L Validation using certied reference [22]
materials
Fe3O4@ZIF-8@MIP (-) SPME HPLC-DAD 4 estrogens Fish, pork 7497 0.4211.65 g/Kg Comparison with Fe3O4@SiO2@MIP and [23]
commercial available SPME bers. E2
as template
Cu3(BTC)2/GO (15 mg) dSPE Square wave Luteolin Tea 97102 0.23 g/L [24]
voltammetry
Fe3O4@Cu3 (BTC)2 (-) m-dSPE FAAS Cd(II), Pb(II) Fish 93103 0.21.1 g/L [25]
MOF-199/GO (-) HS-SPME GC-ECD 8 OCPs Water convulvus, longan 72108 0.00230.0069 g/L Comparison with commercial bers [26]

205
206 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
3. Magnetic and non-magnetic nanoparticles
NPs have gained a lot of importance in all branches of Chemis-
try, including that of Analytical Chemistry, in which they have been
used both as stationary phases and as sorbents in sample extrac-
tion techniques [27,28], becoming one of the most relevant
nanomaterials so far in this eld. In this sense, those NPs which show
magnetic properties have aroused great interest, since they greatly
simplify the extraction process, saving time due to their capacity
to be easily isolated from the sample matrix by the action of an ex-
ternal magnetic eld.
As is well known, the synthesis of NPs, in particular that of mag-
netic NPs (m-NPs), presents two principal problems: they tend to
form agglomerates and they are chemically active, which involves
a loss of magnetism. Furthermore, their high extraction capacity may
also make them inappropriate to be used as extraction sorbents when
complex matrices are analysed. Regarding these facts, it is usual to
include an additional step at the end of the synthesis process, which
involves their protection with an organic (i.e. surfactants or poly-
mers) or inorganic (i.e. silica, carbon including graphene and carbon
nanotubes (CNTs), alumina, etc.) impenetrable layer, resulting in
a core-shell structure [29]. The wide variety of coating materials
currently available has allowed the production of more selective sor-
bents to be used in analytical applications, especially when complex
matrices like foods want to be analysed. Table 2 compiles a good
number of papers in which NPs (with or without coatings) have been
used as sorbents for the extraction of different types of com-
pounds from food samples. Such works have been classied
according to the coating used.
Despite the fact that coated NPs have been mostly used in this
eld as a result of their high selectivity, some interesting applica-
tions can also be found in the literature in which non-coated NPs
have been used with satisfactory results [30,31]. In these articles,
m-dSPE was applied, using Fe3O4 m-NPs as sorbents [30,31] for the
extraction of sulfonamides from milk [30], and sudan dyes from chilli
oil, chilli powder and tomato paste [31], obtaining recovery between
70 and 120% for all of them. For their determination, HPLC with UV
detection was employed in both cases, achieving LODs of 10 g/L
[30] and 1020 g/kg [31], respectively.
Regarding the application of coated NPs (see Table 2) it seems
clear that polymeric shells are one of the most usual in food
sample analysis [3246], probably due to their high stability in a
wide pH range, which results in a great retention capacity. Among
polymeric coatings, molecularly imprinted polymers (MIPs)
[3235,3739,41,42,4446] stand out above the rest, because of their
high selectivity, especially when complex matrices are analysed. Some
examples include the use of vanillin or sulfamethazine as template
molecules. However, other polymeric coatings have also provided in-
teresting results like ionic imprinted polymers (IIP) [40], polydopamine
[36] or polypyrrole (PPy) [43]. Most of these polymers have been com-
bined with Fe3O4 NPs [3238,4045] in order to apply them as sorbents
in m-dSPE procedures, though some authors have also covered SiO2
NPs to be employed in dSPE [46] or SPE [39] processes. It is worthy
to mention that the polymer normally coats the NP directly. In spite
of this, it is also frequent to prepare a rst coating layer of SiO2 to
join them. In this sense, authors have developed different ways to
carry out the combination of both materials. This is the case of the
work of Zhao et al. [43] in which m-NPs and PPy nanowires were
synthetized separately, and then combined by vortex agitation, achiev-
ing a spontaneous assembly of these two materials to form m-PPy
nanowires. Another example is the synthesis process proposed by
Wang et al. [44] who carried out the formation of the MIP over a pre-
vious dendrimeric structure of poly(amidoamine) (PAMAM)
synthesized around the m-NPs in order to improve the imprinting
eciency. Fig. 1 shows a scheme of the synthesis process of the Fe3O4@
SiO2@MIP NPs based on the PAMAM grafting used in that work.
Polymer-coated NPs have been applied for the analysis of a wide
variety of different analytes, including antibiotic compounds
[38,41,45,46], endocrine disruptors [32,36,39], pesticides [43], sul-
fonylurea herbicides [33], etc., from a large number of matrices,
comprising milk [32,34,37,41,45,46], chicken meat [38], sh [40],
or drinks [36,39,43], among others. For analyte determination
both HPLC and UHPLC, have been used in almost all cases
[3234,3639,41,42,44,46] coupled to UV or MS detectors, though
GC-MS [43], inductively coupled plasma optical emission spec-
trometry (ICP-OES) [40] and UV/Vis [45] have also been employed.
The combination of these sorbents and the mentioned determina-
tion techniques have allowed recovery in the range of 70120% and
LODs between 17.4 ng/L and 40.6 g/L.
Among the numerous combinations between m-NPs and MIPs,
it is noteworthy to mention an interesting alternative developed by
Zhao et al [35]. In this work, authors proposed the use of a new
sorbent, which they described as a coreshell nanoring amino-
functionalized magnetic MIP (CS-NR-Mag-MIP), for the extraction
of 22 sulfonamides from chicken breast muscle in a dSPE proce-
dure prior to their analysis by ultra-fast liquid chromatography (UFLC)
with MS detection. This sorbent showed very good extraction ca-
pacity and selectivity, apart from being easy to prepare and
regenerate.
Although they are not as popular as NP polymeric coatings, ionic
liquids (ILs) have also been used in this eld. Previously published
applications have combined ILs with m-NPs of Fe3O4 formerly
covered with SiO2 in order to promote a suitable bonding between
both materials [47,48]. Such sorbents have been employed in m-dSPE
procedures for the extraction of linuron (Fe3O4@SiO2@[OMIM]PF6)
[48] and rhodamine B (Fe3O4@SiO2@[OMIM]PF6) [47] from fruits and
vegetables [48] and spices [47], respectively. The determination of
such target analytes has been carried out by use of spectrophoto-
metric detection [48] and HPLC-UV [47]. As can be seen in Table 2,
the application of IL-coated m-NPs has allowed recovery values
between 70 and 120% and LODs lower than 5 g/L in all work.
It is also worthy to comment the work of Zheng et al. [49] who
used a polymeric IL (PIL) as coating to cover m-NPs, creating a
sorbent which combines the good extraction properties of poly-
mers and ILs with the magnetic properties of Fe3O4 NPs. Authors
applied this sorbent with success for the extraction of a group of
four organophosphorus pesticides from tea drinks and their sub-
sequent determination by HPLC-UV, obtaining high recovery with
LODs of a few g/L.
Surfactants, which have been widely used in sample prepara-
tion for the extraction of numerous organic and inorganic compounds
because of their high adsorption capacity, have also been com-
bined with m-NPs to create sorbents with a high surface area, high
chemical stability and good magnetic separation. Despite their good
properties, their use in food analysis has been quite limited, there
being very few papers in the literature [50,51]. In this sense, only
SDS [50] and tetradecanoate [51] have been used to coat m-NPs of
Fe3O4. In this case, they have been used as sorbents for the extrac-
tion of heavy metal ions (1-(2-pyridylazo)-2-naphthol [PAN] was
used as a complexant agent) [50] and BPA [51] from milk powder
[50] and soft drinks [51], respectively, carrying out an m-dSPE pro-
cedure. Due to the different nature of the studied analytes, techniques
such as ame atomic absorption spectrometry (FAAS) [50] and HPLC-
MS [51] were employed for their determination, accomplishing LODs
between 7 ng/L and 2 g/L. Recovery in the range of 70120% was
obtained.
Apart from the use of the previous coatings, a very usual prac-
tice implies the functionalization of the surface of the NPs with
molecules that may act as ligands, being generally used as selec-
tive sorbents for the extraction and preconcentration of heavy
metallic ions. For this purpose, Fe3O4 [54,59,61,64], SiO2 [70] and
Al2O3 [55] NPs have been coated with dipyridile amine groups [59],
Table 2
Applications of NPs as sorbents used for the analysis of food matrices

Non-coated NPs

Nanomaterial Sample Determination Analytes Matrix Recovery % LODs Comments Reference

treatment technique

Fe3O4 (0.2 g) m-dSPE HPLC-UV Sulfadiazine, Milk 93102 10 g/L [30]

sulfathiazole
Fe3O4 (0.5 g) m-dSPE HPLC-UV Sudan dyes Chilli oil, chilli powder, 93111 1020 g/kg [31]
tomato paste

Polymeric coating

Nanomaterial Sample Determination Analytes Matrix Recovery % LODs Comments Reference

treatment technique

J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220

Fe3O4@MIP (100 mg) m-dSPE UHPLC-UV 17-E2 Milk 8992 0.01 g/L 17-E2 used as template [32]
Fe3O4@SiO2@MIP (100 mg) m-dSPE HPLC-UV 4 sulfonylurea Rice grain 7392 2.633.82 g/kg BSM used as template [33]
herbicides
Fe3O4@SiO2@MIP (20 mg) m-dSPE HPLC-UV Vanillin Bread, milk powder, 8396 40.6 g/L Vanillin used as template [34]
biscuit, chocolate
Coreshell nanoring amino- m-dSPE UFLC-MS/MS 22 sulfonamides Chicken breast muscle 85112 0.0040.030 g/kg [35]
functionalized magnetic
molecularly imprinted polymer
(CS-NR-Mag-MIP) (15 mg)
Fe3O4@Polydopamine (-) m-dSPE HPLC-MS/MS 4 aatoxins Red wine 91108 1.23.1 ng/L [36]
Fe3O4@MIP (20 mg MIP and m-dSPE HPLC-UV 3 uoroquinolones Milk 94124 1.83.2 g/kg SupelMIPTM SPE-Fluoroquinolones [37]
20 mg m-NPs)
Fe3O4@SiO2@MIP (-) m-dSPE HPLC-UV 4 sulfonamides Chicken meat 9599 0.5150 g/kg Sulfamethazine used as template [38]
SiO2@MIP (100 mg) SPE HPLC-UV BPA Drinks (herbal tea, soda, 99105 3 g/L TBBPA used as dummy template [39]
green tea), fresh fruit
(apple, pear, pitaya)
Fe3O4@SiO2@IIP (10 mg) m-dSPE ICP-OES Hg(II) 15 sh samples 98103 0.03 g/L Accuracy determined with [40]
certied reference materials
Hg(II) used as template
Fe3O4@MIP (50 mg) m-dSPE HPLC-UV/Vis Tetracyclines Milk 7594 7.419.4 g/kg Doxycycline used as template [41]
Fe3O4@SiO2@MIP (50 mg) m-dSPE HPLC-UV/Vis Acid orange II Cured meat, red pepper 7094 17.41 ng/L Acid orange II used as template [42]
powder
Fe3O4@polypyrrole nanowires m-dSPE GC-MS 11 pesticides Black tea, green tea, peach 63108 0.030.09 g/L TPP used as IS [43]
(2 mg) juice, orange juice
Fe3O4@SiO2@MIP based on PAMAM m-dSPE HPLC-UV Glibenclamide Health foods 8294 1.56 g/L Glibenclamide used as template [44]
grafting (20 mg)
Fe3O4@SiO2@MIP (50 mg) m-dSPE UV-Vis Metronidazole Milk, honey 8697 8.56 g/L Metronidazole used as template [45]
SiO2@MIP (100 mg) dSPE HPLC-UV 6 sulfonamides Milk, eggs 7089 for SDZ 2.8114.6 g/L Accuracy evaluated only for SDZ [46]
and SMO and SMO
SMO used as template

Ionic liquid coating

Nanomaterial Sample Determination Analytes Matrix Recovery % LODs Comments Reference

treatment technique

Fe3O4@SiO2@[OMIM]PF6 (0.1 g) m-dSPE HPLC-UV Rhodamine B Chili powder, Chinese 99101 0.08 g/L - [47]
prickly ash
Fe3O4@SiO2@[OMIM]PF6 (0.1 g) m-dSPE UV/Vis Linuron Lettuce, apple 9599 5 g/L - [48]
Fe3O4@SiO2@PIL (60 mg) m-dSPE HPLC-UV 4 OPPs Tea drinks 81113 0.01 g/L - [49]
(continued on next page)

207
 208
Table 2
(continued)

Surfactant coating

Nanomaterial Sample Determination Analytes Matrix Recovery % LODs Comments Reference

treatment technique

Fe3O4@SiO2@SDS (50 mg) m-dSPE FAAS Cd(II), Pb(II) Milk powder - 0.1472.02 g/L PAN used as complexing agent [50]
Fe3O4@hemimicelles of m-dSPE HPLC-MS/MS BPA Soft drinks 91105 7 ng/L BPA (ring-13C12) as IS [51]
tetradecanoate (200 mg)

Miscellaneous

Nanomaterial Sample Determination Analytes Matrix Recovery % LODs Comments Reference

J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220

treatment technique

SiO2@NiO (200 mg) SPE HPLC-MS 9 benzimidazoles Egg, milk 76123 0.32.2 g/kg Thiabendazole-d4 used as IS [52]
-Fe2O3@thermophilic bacteria SPE ICP-OES Pb(II), Cd(II) Honey, rice, lentil, potato, 9699 0.060.07 g/L Reference materials were used to [53]
(250 mg) hazelnut, black tea validate the method
Fe3O4@SDS@diphenyl carbazone m-dSPE FAAS Cd(II) Green tea, lettuce, tobacco, - 3.71 g/L [54]
(0.1 g) ginseng, rice, spice, carrot
Al2O3@ligand (8 mg) dSPE GFAAS As(III), As(V) Rice, chicken meat, cow 9198 1.97 ng/L Reference materials and rock [55]
milk samples used to validate the
methodology
Fe3O4@aptamer (-) dSPE FD Oxytetracycline, Pork, milk, honey 7795 0.850.92 g/L [56]
kanamycin
Fe3O4@oleic acid (60 mg) VA-m-dSPE FD 4 aatoxins Pistachio nuts 92100 0.021 g/kg [57]
Fe3O4@eggshell membrane m-dSPE FD Al(III) Tea, cocoa powder, tomato 99105 0.2 g/L Validated with a standard [58]
(200 mg) paste reference material
Fe3O4@SiO2@dipyridile amine m-dSPE FAAS Pb(II) Two rice samples, baking 97102 0.7 g/L Accuracy evaluated with standard [59]
groups (10 mg) powder, wheat, corn, beet, reference material
carrot, potato, radish,
turnip
Fe3O4@TMSPT-AMT (100 mg) m-dSPE Enhanced Aatoxin M1 Milk 9296 0.01 g/L [60]
spectrouorimetry
Fe3O4@PTES-PAR (25 mg) m-dSPE FAAS Cu(II), Pb(II) Cantaloupe, apple, grape, 92113 0.070.7 g/L Certicate reference materials [61]
green beans used to evaluate the accuracy of
the methodology
Functionalized TiO2 HF (2 mg) HF-SPME UV/Vis Tylosin Milk 8999 0.21 g/L [62]
Fe3O4@SiO2@C18 (17 mg) m-dSPE GC-MS 20 OCPs, 6 PCBs Milk 79116 0.10.3 g/L [63]
Fe3O4@SiO2@Schiff base (50 mg) m-dSPE FAAS Pb(II) Rice, sh, ore 97102 0.441 g/L [64]
Fe3O4-Au@antibodies (23 mg) m-dSPE Dynamic long- Soy-protein Soy milk, chocolate 80107 0.35 mg/L [65]
wavelength avoured soy milk
uorometry
Fe3O4@Si-C8/C18 (10 mg) m-dSPE LC-MS/MS 3 veterinary drugs Fish 9295 - CAP-d5 used as IS [66]
m-NPs@baicalin (-) m-dSPE HPLC-MS/MS Isoavones Soymilk 98102 0.030.05 mg/kg Calycosin as IS [67]
Amine functionalized mesoporous m-dSPE GC-FID 8 free fatty acids Oil 81118 7.2226.26 g/L Margaric acid as IS [68]
Fe3O4 m-NPs (20 mg)
-Fe2O3@carboxyl group@Aptamer m-dSPE HPLC-FD Ochratoxin A Cereal products, wheat 6790 0.30.5 g/kg Reference material was analyzed to [69]
(-) our, coffee evaluate the performance of the
proposed method
SiO2@PAN (20 mg) dSPE UV/Vis Pb(II) Potato chips, biscuits - 0.63 g/L - [70]
 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
Fig. 1. Preparation scheme of MNs@PAMAM and Gb-SMIPs. Reprinted from [44] with the permission of John Wiley and Sons.
4-(2-pyridylazo) resorcinol [61], a Schiff base [64], 1-(2-pyridylazo)-
2-naphthol (PAN) [70], diphenyl carbazone [54] and other organic
ligands [55], principally for the selective dSPE of divalent cations,
such as Pb(II) [59,61,64,70], Cu(II) [61] and Cd(II) [54], though As(III)
and As(V) [55] have also been analyzed. Metals have been ana-
lyzed using these particular NPs in cereal [59], vegetable [54,59,70],
fruit [61], sh [64], tea [54], spice [54], chicken meat [55] or milk
samples [55], among others. Concerning their determination, and
as is usual, FAAS has been the most used technique [54,59,61,64],
as well as graphite furnace atomic absorption spectrometry (GFAAS)
[55]. In relation to the accuracy of the developed methods, recov-
ery in the range of 70120% has been obtained in most work, using
certied reference materials to evaluate quality parameters in some
of the studies [55,59,61]. LODs lower than 4 g/L have been achieved
in all cases.
Leaving aside the use of organic ligands, some authors have also
proposed very interesting alternatives for the extraction of metal
ions. Abdolmohammad-Zadeh et al. [58] have combined Fe3O4 NPs
with small pieces of eggshell membrane by means of a mechani-
cal process. These magnetic eggshell membranes were applied as
m-dSPE sorbents for the extraction of Al(III) from tea, cocoa powder
and tomato paste achieving recovery between 99 and 105%. The anal-
ysis of certied reference materials was developed to demonstrate
the accuracy of the methodology. Fluorometric determination was
employed, with an LOD of 0.2 g/L. It is also worthy to comment
the paper of zdemir et al. [53] in which authors proposed the
coating of -Fe2O3 NPs with a biosorbent formed by dead cells of
209
Geobacillus galactosidasius to be used as an SPE sorbent for the ex-
traction of Pb(II) and Cd(II) from honey, rice, lentil, potato, hazelnut
and black tea. Recovery in the range of 9699% was obtained. To
determine the studied analytes, ICP-OES was employed obtaining
LODs between 0.06 and 0.07 g/L.
In the literature, it is also quite common to nd other
functionalizing molecules adsorbed onto the surface of the NP for
the selective interaction with a particular compound or a family of
compounds. Concerning their application for food analysis,
functionalizing groups such as 3-(trimethoxysilyl)-1-propanethiol
modied with 2-amino-5-mercapto-1,3,4-thiadiazole [60], hydro-
carbon chains (C8 or C18) [63,66] or amine groups [68] have been
generally used to cover Fe3O4 NPs prior to their use and applied in
m-dSPE procedures for the extraction of mycotoxins [60], organo-
chlorine pesticides (OCPs) [63], (PCBs) [63], free fatty acids [68] and
veterinary drugs [66]. Regarding the type of samples, milk [60,63],
oil [68] and sh [66] have been analyzed, using techniques such as
enhanced spectrouorimetry [60], GC-MS [63], GC-ame ioniza-
tion detection (FID) [68] and LC-MS [66] for their determination,
with LODs lower than 30 g/L for all of them. Recovery in the range
of 70120% was obtained, using internal standards (ISs) in some cases
[66,68].
In nature, there is a wide variety of compounds which show an
extraordinary selectivity for certain molecules. On occasion, these
kinds of molecules have been selected to cover NPs trying to take
advantage of their exceptional recognition capacity to create a coating
with a very high selectivity and extraction capacity. In this sense,
210 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
Fig. 2. Comparison of SiO2@NiO and SiO2 for the extraction of benzimidazoles. The
milk sample solution spiked with benzimidazoles at a concentration of 500 ng/g was
used, and a total of three replicates were performed in the comparison. Reprinted
from [52] with the permission of ACS Publications.
it is possible to nd work in which baicalin has been used for the
specic extraction of isoavones from soymilk [67]; aptamers have
been applied to extract ochratoxin A from cereals, wheat our and
coffee [69] or oxytetracycline and kanamycin from samples of pork,
milk and honey [56]; soy-protein has been extracted from soymilk
using antibodies [65]; and oleic acid has allowed the isolation of
aatoxins from a pistachio nut matrix [57].
Finally, it is worthy to comment two papers which make use of
NPs in an unusual way. This is the case of the paper published by
Sun et al. [52]. These authors have placed NiO NPs onto the surface
of SiO2 particles using a liquid-phase deposition process. They have
applied this composite to package an SPE cartridge in order to extract
nine benzimidazoles from egg and milk samples and their subse-
quent HPLC-MS analysis, achieving recovery values in the range of
76123% and LODs between 0.32.2 g/kg (thiabendazole-d4 was
used as IS). Fig. 2 shows a comparison of the recovery percentages
obtained when NiO NPs are included as part of the extraction sorbent
and when only SiO2 particles are used for the extraction of benz-
imidazoles. As can be seen, the extraction capacity of SiO2 NPs is
considerably lower than those coated with NiO NPs. This data shows
that the extraction is principally due to NiO NPs rather than SiO2.
Meanwhile, Sehati et al. [62] proposed the application of TiO2
photolytically activated and dispersed in 1-octanol as part of the
organic acceptor phase in an HF for the extraction of tylosin from
milk. Despite the simplicity of the extraction device as well as the
use of UV-Visible detection, the inclusion of such NPs in the organic
phase allowed achieving a high enrichment factor, with recovery
in the range of 8999%, and an LOD value of 0.21 g/L.
4. Carbon nanotubes
Carbon nanotubes (CNTs), both single (SWCNTs) and multi-
walled (MWCNTs) forms, have been reference nanomaterials since
their rst report in 1991 [71]. As is well known, they can be de-
scribed as nanoscale-tubes produced by the scrolling up of graphene
sheets. They present specic characteristics from a physical and chem-
ical point of view that have made them potentially useful for many
applications in different elds. Among these particular character-
istics could be highlighted their high tensile strength, thermal
conductivity, stability and resilience, their variable electronic prop-
erties (they can be excellent conductors or semiconductors depending
on the structural conformation of the graphene sheets), their ability
to establish interactions of different nature with both organic and
inorganic species and the combination of small size and immense
surface area that provide them a large sorptive mass capacity [72,73].
CNTs have been widely applied in Analytical Chemistry for the
preparation of electrochemical sensors (which is an application that
has experienced a sharp increase), polymeric membranes for l-
tration, as stationary phases in chromatographic applications, as
matrices for matrix-assisted laser desorption/ionization (MALDI),
as sorbents in pre-treatment procedures, etc [74]. Particularly, these
materials have been widely applied as sorbents in the food analy-
sis eld; in fact, their comparison with conventional/commercial
sorbents like, for example, C18, hydrophilic-lipophilic balance co-
polymer (HLB) or Strata-X have been widely studied demonstrating
their known advantages [73]. Table 3 compiles the most recent work
accomplished in this eld since there are previous revisions of the
application of CNTs in Analytical Chemistry, in which it is possible
to nd articles related to Food Analysis [3,7274]. As can be seen
in this table, and according to previous review articles, diverse pro-
cedures such as MSPD [83], SBSE [94], SPME [80,95] or carbon
nanotube lm (CNTF) microextraction [79] have been applied for
the analysis of organic and inorganic analytes in complex matri-
ces such as vegetables, fruit, honey, sh, tea or coffee, among others.
However, the majority of these applications have been carried out
using SPE procedures to analyse both organic [1,7578,8183,85,89]
and inorganic [84,8688] analytes and applying both its conven-
tional [84,8689] and its dispersive (dSPE) approach [7578,81,82,85].
The latter (dSPE) considerably simplies the procedure since the
sorbent is not retained in a column or cartridge but is dispersed in
the sample extract, decreasing the extraction time without losing
effectiveness. Another interesting SPE approach applied to the anal-
ysis of food samples is dSPE in which very low amounts of sorbent,
in the range of micrograms and a few milligrams [75,81,82] are used,
thanks to the large surface area and high extraction capacity of this
kind of material. This modality clearly reduces the extraction time
and also decreases the cost [96].
The determination of inorganic analytes usually entails the mod-
ication of CNTs in order to improve their selectivity and extraction
capacity through covalent and non-covalent modications. In this
sense, several changes have been developed in these kinds of sorbent
through their oxidation [97], the inclusion of pyridine groups [87]
or an IIP [88] in their structures as well as preparing polymeric com-
posites [84], among others. Interesting work was carried out by
Ghorbani-Kalhor et al. [84], who showed that the preparation of a
nanocomposite of MWCNTs and poly(N-phenylethanolamine)
allowed the selective extraction of Pb(II) ions from fruits (Citrus
limetta, kiwi, pomegranate) and sh by SPE prior to its determina-
tion by FAAS. In fact, the recovery of Pb(II) in the presence of 13
other transition ions ranged between 96 and 99% with LODs of 0.8
10 g/L. The extraction tolerance ratio, which is dened as the
maximum concentration ratio (concentration of ions/concentration
of Pb(II)) that allows an ecient extraction of this species, ranged
from 700 to 10000. On the contrary, the use of pristine CNTs for the
extraction of inorganic analytes has also been applied but, in these
cases, it is necessary to add a chelating agent, which allows the for-
mation of a neutral complex which can establish Van der Waals
forces or hydrophobic interactions with the non-modied sorbent.
In this sense, Sweileh et al. carried out the extraction of Al(III) ions
from Arabian food products, previous determination by FAAS ob-
taining an LOD of 6.9 g/L and recovery in the range of 7693%.
However, previous complexation with a chelating agent (D-mannitol)
was necessary to avoid the low selectivity of the pure sorbent and
to increase the extraction capacity of MWCNTs [86,98]. In fact,
authors were able to demonstrate that when the ratio of chelating
agent and MWCNTs was 1:1, recovery was around 30%, achieving
Table 3
Applications of CNTs as sorbents used for the analysis of food matrices

Nanomaterial Sample Determination Analytes Matrix Recovery LODs Comments Reference

treatment technique %

MWCNTs-OH dSPE HPLC-DAD Thiabendazole Fruit juice 93104 2.6 g/L Comparison between MWCNTs and [75]
(-) MWCNTs-OH
(7 mg)
IL@MWCNTs US-dSPE HPLC-UV Rhodamine B Grape and blueberry juice, 8596 0.28 g/L [76]
(o.d. < 8 nm) Wine, chili oil
(15 mg)
MWCNTs dSPE HPLC-DAD 25 polyphenols Multioral and cactus honey 90101 - [77]
(-)
(1000 mg)
MWCNTs dSPE UHPLC-MS 22 phenols Monooral, multioral and 90100 - [78]
(-) cactus honey
(1000 mg)
DWCNTs CNTF DCBI-MS/MS Sudan dyes (I-IV), Chili oil 80110 1.421 g/Kg [79]
(-) microextraction rhodamine B

J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220

(-)
DWCNTs@PANI SPME HPLC-UV Thymol, tarvacrol Honey, savory, thyme 95119 600800 g/L [80]
(o.d. < 510 nm)
(10 mg)
MWCNTs dSPE UHPLC-MS/MS 16 amide fungicides Cabbage, celery, strawberry, 7299 3 g/Kg Comparison between MWCNTs with [81]
(o.d. < 8 nm) grape different characteristics
(10 mg)
MWCNTs dSPE CE-DAD 6 pharmaceuticals Tea, wine 71105 58157 g/L [82]
(o.d. 815 nm)
(20 mg)
Chitosan-MWCNT-o MSPD HPLC-UV Acrylamide Potato, our 8595 1.5 g/L [83]
(o.d. 60100 nm) (-)
PNPEA/MWCNTs SPE FAAS Pb(II) Citrus limetta, kiwi, 9699 0.810 g/L Validation using certied reference [84]
(-) pomegranate, sh materials
(100 mg)
MWCNTs dSPE HPLC-DAD 10 phenolic acids, Honey 8996 1541 g/L [85]
(o.d. < 8 nm) 9 avonoids, 6 phenols
(1 g)
MWCNTs SPE FAAS Al(III) Mansaf, kofta, tabboola, 7693 6.9 g/L Complexation with D-mannitol [86]
(o.d. 60100 nm) (-) hummous, bread, tea, coffee
Pyridine-MWCNTs SPE FAAS Cu(II) Cantaloupe, apple, grape, 95105 0.65 g/L [87]
(d. 1040 nm) nectarine, green beans
(200 mg)
IIPs-MWCNTs SPE FAAS Cd(II) Lettuce, dill, onion, spinach, 96 1.3 g/L Validation with certied reference [88]
(-) parsley, cabbage, tea materials
(200 mg)
BP-MWCNTs-OH + HLB SPE HPLC-MS 4 cobalamins Milk 44100 0.41.6 g/L Dicyanocobinamide used as IS [89]
(-)
(13 mg)

Combined with other nanomaterials

Fe3O4-MWCNTs-MIP m-dSPE HPLC-DAD Sulfamethoxazole Milk, honey 6880 6.04 g/L Sulfamethoxazole used as template [90]
(d. 60100 nm)
(100 mg)
Fe3O4-MWCNTs - m-SPE GC-FID 2 phthalates Chicken soup plastic packaged 70118 26.336.4 g/L [91]
PVA
(d. 60100 nm)
(1.5 mg)
Fe3O4/MWCNTs m-dSPE FL Thiamine Cereal, wheat our, banana, 90105 0.37 g/L Thiamine derivatized as thiocrome [92]
(d. 320 nm) honey with potassium hexacyanoferrate(III)
(4 mg)
MWCNTs/Fe3O4@SiO2@MIP m-dSPE GC-MS 6 PCBs Fish 73114 0.00280.0068 g/L 3,4-dichlorobenzene acetic acid as [93]

211
(o.d. < 8 nm) template
(50 mg)
212 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
Fig. 3. Electropherograms of blank and spiked wine (left) and tea samples (right) without the application of dSPE (above) and after dSPE application using MWCNTs (middle,
below). Target analytes: 1.- Reserpine; 2.- Chlortalidone; 3.- Indapamide; 4.- Hydrochlorothiazide; 5.-Nifedipine; 6.-Valsartan. Reprinted from [82] with the permission of
the Royal Society of Chemistry.
an increase of 100% when the ratio was established at 20:1. This
alternative has been applied in diverse occasions for the analysis
of food samples with the aim of avoiding CNT modication and sim-
plifying the procedure since only the addition of a chelating agent
is necessary to accomplish the extraction.
Concerning organic analytes, diverse modications such as ox-
idation, combination of specic polymers, addition of MIPs or
combination with ILs [72,73] have also been developed obtaining
good results. As an example, Xu et al. [75] prepared hydroxyl
functionalized MWCNTs (MWCNTs-OH) to extract the pesticide thia-
bendazole from fruit juices prior to its HPLC-DAD analysis obtaining
an LOD of 2.6 g/L and recovery in the range of 93104%. Authors
demonstrated that the higher extraction capacity of MWCNTs-OH
compared to pristine MWCNTs was based on the fact that OH-
functional groups increase the polarity (and therefore its
hydrophilicity) and the surface sorbent wettability, avoiding their
natural tendency to aggregate, which clearly reduces the active
surface area and decreases the extraction effectiveness, together with
the specic interaction between the functional groups and the target
analytes. Besides the conventional application of CNTs, it has been
recently described the use of buckypaper (BP), a nanoporous mem-
brane based on CNTs, as extraction sorbent since it exhibits all
characteristics of CNTs but also shows two important advantages
over free CNTs: safe handling because CNTs are entangled in a sheet
and higher mechanical stability. In this sense, it is worth mention-
ing the paper of Prez-Fernndez et al. [89], who carried out the
SPE of four cobalamins from milk using two disks of BP composed
by MWCNTs-OH separated by a Teon frit from OASIS HLB. After
evaluating these two sorbents, both separately and in combina-
tion, authors determined that the addition of a little amount
of BP (15 mg) to OASIS HLB resulted in a considerable improve-
ment in extraction eciency. Thus, absolute recoveries higher
than 44% were obtained for all analytes when milk samples were
analysed.
It is doubtless that MWCNTs have been successfully used for the
extraction of a wide variety of compounds from food samples
(Table 3), but it should also be highlighted that they have been suc-
cessfully used, though in fewer occasions, as clean-up sorbents in
complex alimentary matrices such as rice [99], tea [100] or veg-
etables, fruit and nuts [101], among others. In this sense, Zen et al.
[82] carried out the extraction of 6 pharmaceuticals from tea and
wine with 8 mL of ACN followed by dSPE using 20 mg of MWCNTs
prior to their determination by capillary electrophoresis (CE)-
DAD. As can be seen in Fig. 3, the authors showed that MWCNTs
not only present an excellent extraction capacity for the target
analytes but also allow effective removal of the co-existent inter-
fering species, which is extremely important with matrices as
complex as food samples.
As can be concluded from this manuscript, the possibilities of
the application of CNTs in any of their formats to the food analysis
eld is immense due to the great advantages that these kinds of
sorbent present to clean them and to extract target analytes either
directly from them or from their extracts. Such extraction and clean-
up capacity is particularly important when they have to be coupled
 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
or combined with different analytical techniques. In this sense, HPLC-
MS, UHPLC-MS, CE-DAD, GC-MS/MS, GC-ECD, GC-FID, FAAS, GFAAS,
atomic absorption spectroscopy (AAS) and electrothermal atomi-
zation atomic absorption spectroscopy (EAAS) have been applied
with success.
5. Graphene
The use of this material achieved great interest in different elds
after Geim and Novoselov developed an easy method to obtain high-
quality graphene in 2004 [102]. Among its excellent properties
provided by its planar structure, its high thermal and electron con-
ductivity, elasticity, exibility and ultra-high surface area should be
remarked. Particularly in the eld of Analytical Chemistry, the use
of this material has experienced a relevant increase in sorbent-
based extraction methodologies due to the characteristics indicated
above, together with its hydrophobicity, the possibility to be chem-
ically modied, as well as the possibility of establishing -
interactions thanks to its delocalized electrons. Another impor-
tant advantage of graphene versus other sorbent materials is the
fact that it can be easily obtained through the oxidation of graph-
ite to graphene oxide (GO) prior reduction of GO to graphene using
a reducing agent like hydrazine or hydrogen iodide and without using
metal catalysis, which avoids contaminants in the nal products.
Besides, its surface is more active than other relevant carbona-
ceous sorbents such as CNTs since both sides of the planar sheet
of the structure of graphene can take part in the extraction process
whereas for CNTs the inner walls are in most cases inactive due to
steric hindrance [2,103106].
On the other hand, GO usually obtained through graphene ox-
idation by the Hummers method [107], has also attracted much
interest in Analytical Chemistry due to different facts. Among them,
one of the most important is an economic aspect since GO is much
cheaper than graphene and it can be produced on a large scale [108].
Apart from its large surface area and the hexagonal structure of
carbon which it shares with graphene allowing the establishment
of strong interactions with other compounds, GO possesses huge
amounts of oxygen atoms on its surface as epoxy, hydroxyl and car-
boxyl groups that favor its hydrophilicity and, consequently, its
dispersion in aqueous solvents, which has been an obstacle in the
application of graphene as a sorbent for the extraction of organic
and inorganic analytes. In addition, such groups obtained by the ox-
idation process allow GO to establish hydrogen bonds or electrostatic
interactions with diverse compounds, which favors the extraction
process. In fact, graphene is considered an excellent hydrophobic
sorbent for its application in reverse-phase SPE whereas GO can be
used in normal-phase SPE for the extraction of organic com-
pounds with oxygen groups or metal ions [103,104].
As can be seen in Table 4 the application of graphene or GO in
sorbent-based extraction methodologies used in food analysis,
has been mainly focused on SPE both in its conventional
[109,111,112,114,116,118121,123125] and dSPE [108,112,126130]
approaches as well as SBSE [122] and SPME [113,117] for the anal-
ysis of organic [108,111113,115,117,118,122125,127129] and also
inorganic analytes [109,114,116,119121,126,130].
Despite the large number of excellent characteristics
that graphene and GO present as sorbents, their application
without further modication has only been carried out in a rela-
tively low number of occasions in the food analysis eld
[108,109,112,120,123125]. These methodologies have been almost
exclusively developed for the analysis of organic contaminants in
different samples such as dietary supplements [112], alcoholic bev-
erages [113], cereals [108] and sh [123125] with excellent results
and only a few of them have been applied for the analysis of metal
ions [109,120]. In these cases, as has been previously indicated, it
is commonly necessary to use a chelating agent to favor the ex-
213
traction process as already explained for CNTs. In this way Porjavid
et al. used 3-(1-methyl-1H-pyrrol-2-yl)-1H-pyrazole-5-carboxylic
acid (MPPC) for the complexation of Mn(II) and Fe(II) [120] from
spinach leaves, tea and mineral water. However, Bahram et al. have
recently demonstrated the possibility of extracting Ni(II) from dif-
ferent vegetable samples without any additional help than the use
of graphene alone [109]. Regarding organic analysis, and to the best
of our knowledge, only one paper was based on the application of
SPME [113]. In that case Min et al. [113] carried out the determi-
nation of two contaminants with important volatility differences
(2,4,6-trichloroanisole (TCA) and dibutyl phthalate (DBP)) from red
wine samples by GC-MS after SPME obtaining recoveries in the range
of 9798% and LODs of the method of 0.003 g/L for both analytes.
The SPME ber was prepared by a space resolved sol-gel method
in which both graphene and GO were etched in two different parts
of the wire support creating a ber with two types of sorbent. Studies
showed that the best extraction capacity for TCA was obtained when
graphene was used with the head-space SPME (HS-SPME) ap-
proach whereas for DBP the best conditions were obtained using
GO with direct immersion SPME due to the structural and volatil-
ity differences. This methodology allowed the simultaneous and fast
determination of two important contaminants in red wine thanks
to the separation of the different sorbents in only one ber.
Regarding SPE, some authors have carried out comparative studies
in order to show the advantages of using graphene rather than other
sorbents for the extraction of analytes of different nature includ-
ing sulfonamides [123] and chloramphenicol [125] from food
samples such as sh tissues [123,125]. In both articles, the higher
extraction capacity of graphene versus other sorbents such as C18
or graphite carbon was demonstrated since in these last cases it was
necessary to use higher amounts of sorbent (around 1320 times
higher) to achieve similar recovery values. Regarding MWCNTs,
slightly lower recovery was obtained when they were used, which
was attributed in both articles to the more exible structure of
graphene and to the steric hindrance associated with the CNT tube
structure.
Regarding the application of modied graphene and GO, as well
as their combination with other materials, it is possible to nd a
large number of different methodologies developed for the extrac-
tion of organic [111,115,117,118,122] and inorganic analytes
[114,116,119,121] in different matrices such as cooked food [111,122],
fruit and vegetables [116,118,121], sh and shellsh [111,116,119],
aromatic plants [117], legumes and cereals [114] and honey [115].
The application of these nanomaterials to the analysis of inorgan-
ic analytes was based on modications of their surface with amine
groups (i.e. dipyridyl amine, amine and triamine) with the aim of
solving the limitation of graphene to extract metal ions due to its
lack of selectivity in this case and its low adsorption capacity
[116,119,121]. A different approach was carried out by Islam et al.
for the extraction of Pb(II) from rice, and chickpea prior determi-
nation with FAAS [114]. In that work, authors described the
immobilization of graphene oxide on a chloromethylated polysty-
rene resin through ethylenediamine with the aim of avoiding the
leaching of GO from the SPE column and its irreversible aggrega-
tion, associated to its strong Van der Waals and - stacking
interactions which, consequently, reduce the time of operation during
the adsorption-desorption cycles and the sorbent losses.
Concerning organic analyte determinations, graphene has been
used as a sorbent modier in SPE monolithic columns for the ex-
traction of pesticides from different vegetables [118] in order to
reinforce the mechanical stability of the monolithic polymer and
to improve the adsorption of the target analytes. With the same aim,
sulphonated graphene has been used for doping the polypyrole
coating of SPME bers for the analysis of terpenes [117] improv-
ing the sorbent characteristics such as mechanical durability and
thermal stability as well as the interaction between the sorbent and
Table 4

214
Applications of graphene as sorbents used for the analysis of food matrices

Nanomaterial Sample Determination Analytes Matrix Recovery LODs Comments Reference

treatment technique %

Graphene SPE FAAS Ni(II) Potato, parsley, tomato 99110 0.588 g/L [109]
(10 mg)
GO-MIP SPE HPLC-FD Phloxine B Coffee bean 8992 0.075 g/L Phloxine B was used as template [110]
(2 mg)
Acrylamide@graphene On-line HPLC-UV 6 heterocyclic amines (HAs) Spicy salted duck, baked 66118 0.0007 0.0025 g/L Comparison with graphene, Florisil and C18 [111]
(-) SPE sh, fried chicken stationary phases
GO dSPE UHPLC-MS 3 phenolic compounds Dietary supplements 8698 0.070.21 g/L [112]
(0.2 mg)
Graphene and GO (-) SPME GC-MS 2,4,6-trichloroanisole (TCA), Red wine 9798 0.0003 g/L Best conditions: [113]
dibutyl phthalate (DBP) Graphene for TCA, GO for DBP
Methylated polystyrene- ethylendiamine-GO SPE FAAS Pb(II) Rice, chickpea 100103 2.3 g/L [114]
(20 mg)
C18-graphene HF-LPME HPLC-UV/Vis 4 chlorophenols Honey 88108 <1.5 g/Kg Sorbent used as acceptor phase in the HF- [115]
(0.04 mg) LPME
(3-aminopropyl)triethoxysilane-graphene SPE FAAS Cd(II), Cu(II), Ni(II), Zn(II), Fish, tomato, mushroom, 96100 0.031 g/L [116]

J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220

(50 mg) Pb(II) apple
Sulphonated graphene@polypyrrole HS-SPME GC-MS Terpenes Star anise, fennel 7798 0.07 0.2 g/L [117]
(-)
Poly(BMA@EDMA@graphene) SPE HPLC-UV/Vis 4 pesticides Apple, tomato, orange, 7095 0.9310 g/Kg SPE carried out using a monolithic column [118]
(-) cucumber, grape, rape
Dipyridyl amine@graphene SPE FAAS Cd(II) Fish, oyster, shrimp 99 0.19 g/L Validation using standard reference materials [119]
(100 mg)
GO SPE FAAS Mn(II), Fe(II) Spinach leaves, tea, 96104 0.145 0.162 g/L MPPC was used as chelating agent [120]
(30 mg) mineral water
Amine@graphene, Triamine@graphene SPE FAAS Cd(II), Pb(II) Leek, spinach, onion, 96106 <0.005 g/L [121]
(100 mg) garlic
Graphene-polydopamine-steel stainless SBSE HPLC-FD 6 PAHs Grilled meat 89114 0.00020.05 g/L [122]
(-)
GO dSPE HPLC-FD 4 aatoxins Peanut 85101 0.080.65 g/Kg [108]
(5 mg)
Graphene SPE UHPLC-MS/MS 13 sulfonamides Grass carp sh 7692 0.722.68 g/Kg Comparison with other sorbents (C18, [123]
(15 mg) MWCNTs, graphite carbon)
GO SPE UHPLC-MS/MS Malachite Fresh and ungutted sh 82103 - [124]
(10 mg) green, leucomalachite green
Graphene SPE HPLC-MS/MS Chloramphenicol Fish muscles 92103 0.036 g/Kg Comparison with other conventional sorbents [125]
(20 mg) (C18, MWCNTs)

Combined with other nanomaterials

Fe3O4@GO-DVB-VA m-dSPE FAAS Pb(II), Cd(II), Cu(II), Ni(II), Chili,black pepper, hemp 81100 0.372.39 g/L Reference materials were used [126]
(100 mg) Co(II)
Fe3O4@SiO2@GO-PEA m-dSPE GC-NPD 6 OPPs Apple, grape, pear, bell 90108 0.020.5 g/Kg [127]
(30 mg) pepper, celery.
GO@Fe3O4 m-dSPE HPLC-DAD Tartrazine, allure red, Blend and Strawberry 8996 1016 g/L [128]
(10 mg) amaranth, new coccine juice
GO@Fe3O4@MIP m-dSPE GC-MS 6 PCBs Fish 8094 0.00350.007 g/L 3,4-dichlorobenzidine was used as template [129]
(-)
NH3@Fe3O4@GO m-dSPE FAAS Cu(II) Eggplant, red lentil, 9799 0.9 g/L [130]
(5 mg) mushroom
3D-Graphene@Fe3O4 m-dSPE HPLC-UV Chlorophenols Honey 9399 1.0 - 1.5 g/Kg [131]
(-)
Graphene@Fe3O4 m-dSPE HPLC-FD 4 aatoxins Rice, wheat, sesame 65122 0.0250.075 g/Kg [132]
(10 mg)
MIP@Graphene@Fe3O4 m-dSPE UV 17-E2 Milk powder 84 9.54 g/L [133]
(20 mg)
Graphene@Co3O4 SPE FAAS Pb(II), Cu(II), Fe(II) Kiwi, wheat 95105 <0.81 g/Kg Validation using standard reference materials [134]
(100 mg)
Graphene-SiO2@Fe3O4 m-dSPE GC-MS 6 pyrethroid pesticides Orange, lettuce 90104 0.010.02 g/Kg [135]
(20 mg)
GO@Fe3O4 m-dSPE ECLIA Aatoxin Milk 90120 0.3 g/L Composite preparation with the analyte, [136]
(0.45 mg) sorbent and cadmium telluride quantum dots
and CNTs was necessary for inmunoanalysis
 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
the target analytes. In this case, Zhang et al. demonstrated the in-
crease in the extraction capacity of terpenes from star anise and
fennel when the level of sulphonated graphene doping was in-
creased, obtaining recoveries in the range of 7798% and LODs
between 0.07 and 0.2 g/L. Conversely, in another application de-
veloped by Sun et al. graphene was the substrate modied with C18
[115]. This sorbent was introduced together with octanol inside a
polypropylene HF in an HF-LPME, showing that the reinforcement
of the HF with C18-graphene favored the extraction capacity for the
extraction of 4 chlorophenols from honey samples. Determination
was accomplished by HPLC-UV/Vis obtaining recoveries around 88
108% and LODs lower than 1.5 g/Kg.
As has been seen in this section, graphene and GO show a large
number of advantages with respect to other sorbents for the anal-
ysis of organic and inorganic analytes in food samples. Besides that,
it should be remarked that this sorbent is one of the most applied
in the last few years, and also at extremely low amounts, between
0.04 and 100 mg (with its respective low elution volumes) which
clearly demonstrates the benets, from an environmental point of
view, that the use of these sorbents offer.
6. Combination of different nanomaterials
The diverse advantages that nanomaterials present for food
sample analysis have been exhaustively exposed in this review article.
Taking that into account, the combination of these sorbents can also
present an interesting alternative to increase their effectiveness even
more, as well as to decrease the sample pretreatment time and, con-
sequently, favor the simplicity of the whole extraction process.
In this sense, NPs and specically m-NPs constitute the sor-
bents most widely combined with other materials since, as was
indicated in Section 3, they provide a great number of advantages
such as high stability, high surface area and high sorption capaci-
ty. Besides, they can be easily isolated from the sample matrix thanks
to their trend to be attracted by an external magnetic eld, allow-
ing a great simplication of the extraction process.
Regarding the combination of NPs with carbonaceous sorbents
such as CNTs and graphene, apart from the advantages that NPs
provide, these nanomaterials allow avoidance of the important
problem of aggregation and resistance against liquid ow when the
last of them are used alone as sorbents [92,134]. The combination
of CNTs with NPs has been exclusively focused on their combina-
tion with iron oxide m-NPs for the m-dSPE of organic compounds
in different samples such as honey [90,92], drinks of diverse nature
[90,137], cereals [92], fruit [92], sh [93], meat [91] or eggs [138]
with sorbent amounts in the range of 1.5100 mg. Some of these
applications were based on the extraction capacity of pristine
MWCNTs as it is the methodology developed by Tarigh et al. [92],
who carried out the simultaneous clean-up, extraction and
preconcentration of thiamine (vitamin B 1 ) after its in situ
derivatization as thiochrome from a great variety of samples such
as cereals, wheat our, banana and honey of traces through an ul-
trasound assisted-m-dSPE (US-m-dSPE) using only 4 mg of
sorbent. The great effectiveness of the procedure allowed the direct
determination of the analyte by uorescence detection (FD), ob-
taining recovery in the range of 90105% and an LOD of 0.37 g/L.
Authors demonstrated that the magnetic approach greatly im-
proved the separation rate while avoiding the time-consuming
passage through the column. Besides, the sorbent could be reused
up to ten times without loss of eciency using a washing step con-
sisting of 1-propanol/water between the extraction cycles, which
is very important from an economic and environmental point of view.
However, some applications have also combined a third mate-
rial to the NP-CNTs like, for example MIPs [90,93] or supporting
polymers [91] with the aim of increasing the extraction eciency
of the applied sorbent. In this sense Zhao et al. [90] synthesized a
215
MIP supported on an Fe3O4-MWCNT composite to favor the binding
capacity and site accessibility of the MIPs as well as to avoid the
heterogeneous distribution of the binding sites, slow binding ki-
netics, low binding capacity and selectivity, and poor site accessibility
that occur when MIPs are synthetized by bulk polymerization. The
prepared sorbent allowed the extraction of sulfamethoxazole from
milk and honey samples prior to their determination by HPLC-
DAD, obtaining recovery of between 60 and 80% and an LOD of
6.04 g/L. An interesting example of the preparation of NPs-
MWCNT sorbents supporting in polymeric structures is the work
developed by Makkaliang et al. [91] in which poly (vinyl alcohol)
(PVA) cryogel was used to prepare nanocomposite microbars (Fe3O4-
MWCNTs-PVA) with 1.5 g of sorbent to carry out the determination
of 2 phthalates in chicken soup plastic packaged samples using GC-
FID for the separation and detection of the analytes. For the
extraction, a microbar was introduced in a vial containing 1 mL of
the sample extract as is shown in Fig. 4. The vial was closed and
sonicated for 30 min to improve extraction. Then, the sample was
discarded with the help of an external magnet and the analytes were
eluted using 1 mL of acetone:hexane (1/1, v/v) assisted by ultra-
sound for 20 min. Finally, the sorbent was separated from the elution
solvent using again a permanent magnet, dried, re-dissolved in
0.2 mL of ethyl acetate and 1 L was injected in the GC-FID. This
methodology allowed recovery in the range of 70118% and LODs
between 26.3 and 36.4 g/L.
Concerning the combination of graphene or GO with NPs, it has
been applied in a few studies [126,130,134]. As an example, Yavuz
et al. carried out the analysis of inorganic compounds such as
Pb(II), Cu(II) and Fe(II) from vegetables and fruits using 100 mg of
a nanocomposite composed of graphene and Co3O4 [134]. In this
work Yavuz et al. evaluated the application of dSPE and conven-
tional SPE obtaining good extraction capacity in both cases. Authors
showed the advantages that the prepared nanocomposite pres-
ents for the extraction of metal ions from such complex matrices
to others previously evaluated like, for example, zincon-modied
activated carbon, ethylenediamine-MWCNTs, activated carbon modi-
ed with 2-((2-aminoethylamino)methyl) phenol, silica gel modied
with curcumin or nano-sized MgO2-MWCNTs, in terms of adsorp-
tion and elution speed, adsorption capacity and the pre-concentration
factor. However, in general terms, the applications of this combi-
nation of nanomaterials has been focused principally on the
determination of organic compounds from honey [131], rice and
cereals [132], milk [133,136], fruit and vegetables [127,128,135] and
sh [129] using Fe3O4 NPs together with graphene or GO for the ap-
plication of m-dSPE. Most of these articles used the sorbent without
further modications, however some of them have also described
the later modication of the graphene or GO layer using amine
groups [127,130] or MIPs [129,133] as carried out by Ning et al. [133],
who included the addition of an MIP for the extraction of 17-
estradiol (17-E2) from milk powder prior to UV detection. Recovery
of around 84% and an LOD of 9.54 g/L were obtained. Authors in-
dicated that the combination of the MIP-GO composite with
magnetic NPs favoured 17-E2 separation from the sample extract
and elution solvent in the different steps of the procedure and, con-
sequently, avoided the problems associated with the homogeneous
dispersion of MIP-GO which makes it dicult to separate them by
centrifugation. An interesting example of a non-modied combi-
nation of m-NPs and GO is the simple, exible and highly selective
methodology developed by Gan et al. [136] based on the separa-
tion, preconcentration and detection of Aatoxin M1 from milk
samples using GO@Fe 3 O 4 as sorbent and including another
nanomaterial, as quantum dots (QDs), to improve their detection,
for which an ultrasensitive electrochemiluminescent immunoas-
say (ECLIA) was used. This technique resulted to be very sensitive
for the determination of ultratraces of the target analyte in food,
obtaining an LOD of 0.3 g/L.
216 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
Fig. 4. Description of the m-MWCNTs-PVA-cryogel--SPE procedure for the extraction of phthalate esters (A). Image of a fabricated magnetic-MWCNTs-PVA cryogel--SPE
microbar (B) and the sorbent in the step of adsorption or desorption under the external magnet effect (C). Reprinted from [91] with the permission of Elsevier.
Meanwhile, MOFs have also been combined with different
nanomaterials. They have been mainly combined with iron oxide
m-NPs as m-dSPE sorbents for the extraction of metallic ions such
as Cd(II), Pb(II), Zn(II), Cr(III), Co(II) or Ni(II) from vegetables [21,22],
rice [22], baby food [18] and sh [17,25] samples. The magnetic
properties of this combined nanomaterial have sometimes been
used to join it to a stir bar by magnetic attraction and to use it as a
sorbent in an SBSE process. This approach has been used for the
extraction of PCBs from sh [19] and snakehead [19]. Maya et al.
[20] developed a similar approach, but in their work the stir bar
was only used to isolate the magnetic MOF. Authors developed an
automatic m-dSPE strategy based on the lab-in-syringe concept,
using the stir bar both to retain the sorbent and to facilitate its
dispersion in the sample, favouring the extraction process. Using
this method, they achieved the extraction of malachite green from
sh with high recovery values and LOD in the order of a few mg/L.
Fig. 5 shows a scheme of the automatic in-syringe m-dSPE process
developed.
The combination of MOF and m-NPs (MOF/m-NPs) has been used
not only directly as a sorbent but also as a support to add another
more selective sorbent. Following this principle, Lan et al. [23]
synthetized a new sorbent based on a combination of Fe3O4 m-NPs
and ZIF-8 as a support for an MIP. This composite was electromag-
netically bonded onto the surface of a stainless steel wire creating
a bre which was used in an SPME for the extraction of four
oestrogens from sh and pork samples, obtaining high recovery
values and low LODs.
Besides its combination with m-NPs, MOF/GO composites have
also been used as sorbents in dSPE [24] and HS-SPME [26] for the
extraction of luteolin from tea [24] and OCPs from water convulvus
and longan [26]. These composites meet the high specic surface
area of MOFs and the enhanced dispersive forces of GO which make
them very interesting sorbents to be applied in sample pretreat-
ment [26]. Apart from the above, other nanocomposites have been
used, though in fewer occasions, like that synthesized by M. Wu et al.
[16] in which an MOF was prepared with an IL functionalized
graphene on etched stainless steel wire, using it as a sorbent in an
SPME procedure for the extraction of chloramphenicol and
thiamphenicol from milk and honey samples, prior to their deter-
mination by GC-FID. The synergetic effect of porous MOF and IL@
graphene provided a high adsorption capability and good
reproducibility, with recovery of between 87 and 103% and LODs
in the range of 14.819.5 ng/L.
7. Conclusions
The use of nanomaterials of different nature in Chemistry has
become commonplace because of the extraordinary properties they
show due to their nano-size. In the last few years, this kind of new
material has aroused great interest in Analytical Chemistry appli-
cations, especially to be used as sorbents in extraction techniques
as a result of their high surface-area to volume ratio and their ca-
pacity to be functionalized, which results in more selective sorbents.
These features make them capable of extracting both organic and
inorganic compounds, even at low concentrations, from very complex
matrices like food samples.
In relation to food analysis, MOFs, NPs, CNTs and graphene
have been the nanomaterials most used. However, a wide number
of combinations of two or more of these structures have also
emerged in the last few years, allowing the creation of advanced
nanomaterials.
In spite of their extremely high extraction capacity, and as a con-
sequence of their high porosity, the application of MOFs to food
analysis has been very limited, having been applied to the extrac-
tion of organic compounds from cereals, vegetables and foods of
animal origin, principally in dSPE processes, including dSPE.
In contrast with MOFs, NPs are probably the most widespread
nanomaterial used as a sorbent in extraction procedures. In this
 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
Fig. 5. (A) Scheme of the ow-based instrumental setup. V1 V2, solenoid valves; S1 S2, 5 mL glass syringes; W, waste reservoir. (B) Magnet coated with 10 mg of mag-
netic MOF placed inside a 5 mL glass syringe. (C) In-syringe dispersion of a magnetic MOF facilitated by magnetic stirring. (D) Schematic depiction of the extraction procedure
in syringe 1 (the washing step between extraction and elution is not included). Reprinted from [20] with the permission of ACS Publications.
sense, NPs have been used both directly as sorbents and, especial-
ly, with an additional coating resulting in a more selective core-
shell structure. Among the different types of NPs available, m-NPs
have become the most widely employed, principally because they
are very easy to isolate from the samples/extracts with a magnet.
This fact and the general capacity of NPs to be functionalized make
them very popular. Different coatings have been employed, includ-
ing polymers, ILs or surfactants, having been applied to the analysis
of both organic and inorganic substances in a wide variety of samples
of varying nature.
Besides the above, the use of carbon-based nanomaterials has
also notably increased up to now. In this sense, CNTs, both SWCNTs
and MWCNTs, as well as graphene stand out above any other. The
possibility of the functionalization of these materials, their capac-
ity to establish interactions of different nature with both organic
and inorganic compounds and their high extraction capacity make
these materials very suitable for the extraction of a wide variety
of compounds in a large number of food samples of different origin.
In order to improve the properties of the sorbents, many authors
have also combined different nanomaterials. This practice allows
new materials to be obtained which have the advantages of every
nanomaterial used, making them more suitable for certain appli-
cations. Among the different possibilities, the most popular
composites include m-NPs embedded or deposited onto the surface
of another nanomaterial, due to the advantages that magnetic prop-
erties provide to the extraction process.
Judging by the great number of articles published in which
nanomaterials and combinations of them have been applied to the
extraction of compounds of different nature from diverse food
samples, it seems clear that we are witnessing an important period
in which nanomaterials will play a key role in the development of
new sorbent-based analytical methodologies.
217
Acknowledgements
J.G.S. and B.S.R. would like to thank the Canary Agency of
Economy, Industry, Trade and Knowledge of the Government of the
Canary Islands for the FPI fellowship (co-nanced with an 85% from
European Social Funds). B.S.R. would also like to thank the same
agency for the nancial support for training researchers (co-
nanced with 85% from European Social Funds) given to the
University of La Laguna. This work has been supported by the
Spanish Ministry of Economy and Competitiveness (project
CTQ2014-57195-P).
References
[1] C. Bendicho, I. Costas-Mora, V. Romero, I. Lavilla, Nanoparticle-enhanced
liquid-phase microextraction, Trends Anal. Chem.; TrAC 68 (2015) 7887.
[2] X. Wanga, B. Liua, Q. Luc, Q. Qu, Graphene-based materials: fabrication and
application for adsorption in analytical chemistry, J. Chromatogr. A 1362 (2014)
115.
[3] J. Tian, J. Xu, F. Zhu, T. Lu, C. Su, G. Ouyang, Application of nanomaterials in
sample preparation, J. Chromatogr. A 1300 (2013) 216.
[4] E.B. Bahadr, M.K. Sezgintrk, Applications of graphene in electrochemical
sensing and biosensing, Trends Anal. Chem.; TrAC 76 (2016) 114.
[5] .I. Lpez-Lorente, M. Valcrcel, The third way in analytical nanoscience and
nanotechnology: involvement of nanotools and nanoanalytes in the same
analytical process, Trends Anal. Chem.; TrAC 75 (2016) 19.
[6] R. Sharma, K.V. Ragavan, M.S. Thakur, K.S.M.S. Raghavarao, Recent advances
in nanoparticle based aptasensors for food contaminants, Biosens. Bioelectron.
74 (2015) 612627.
[7] J. Li, Y.-B. Wang, K.-Y. Li, Y.-Q. Cao, S. Wu, L. Wu, Advances in different
congurations of solid-phase microextraction and their applications in food
and environmental analysis, Trends Anal. Chem.; TrAC 72 (2015) 141152.
[8] S. Lin, N. Gan, L. Qiao, J. Zhang, Y. Cao, Y. Chen, Aptamer-functionalized stir
bar sorptive extraction coupled with gas chromatographymass spectrometry
for selective enrichment and determination of poly chlorinated biphenyls in
sh samples, Talanta 149 (2016) 266274.
218 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
[9] S. Lirio, W.-L. Liu, C.-L. Lin, C.-H. Lin, H.-Y. Huang, Aluminum based metal-
organic framework-polymer monolith in solid-phase microextraction of
penicillins in river water and milk samples, J. Chromatogr. A 1428 (2016)
236245.
[10] N. Li, L. Wu, L. Nian, Y. Song, L. Lei, X. Yang, et al., Dynamic microwave assisted
extraction coupled with dispersive micro-solid-phase extraction of herbicides
in soybeans, Talanta 142 (2015) 4350.
[11] N. Li, L. Zhang, L. Nian, B. Cao, Z. Wang, L. Lei, et al., Dispersive micro-solid-
phase extraction of herbicides in vegetable oil with metalorganic framework
MIL-101, J. Agric. Food Chem. 63 (2015) 21542161.
[12] R. dos Anjos de Jesus, L.F.S. Santos, S. Navickiene, M.E. de Mesquita, Evaluation
of metal-organic framework as low-cost adsorbent material in the
determination of pesticide residues in soursop exotic fruit (Annona muricata)
by liquid chromatography, Food Anal. Method. 8 (2015) 446451.
[13] N. Li, Z. Wang, L. Zhang, L. Nian, L. Lei, X. Yang, et al., Liquid-phase extraction
coupled with metalorganic frameworks-based dispersive solid phase
extraction of herbicides in peanuts, Talanta 128 (2014) 345353.
[14] A.S. Barreto, R.L. Da Silva, S.C.G. Dos Santos Silva, M.O. Rodrigues, C.A.
De Simone, G.F. De S, et al., Potential of a metalorganic framework as a new
material for solid-phase extraction of pesticides from lettuce (Lactuca sativa),
with analysis by gas chromatography-mass spectrometry, J. Sep. Sci. 33 (2010)
38113816.
[15] X. Liu, C. Wang, Q. Wu, Z. Wang, Metal-organic framework-templated synthesis
of magnetic nanoporous carbon as an ecient absorbent for enrichment of
phenylurea herbicides, Anal. Chim. Acta 870 (2015) 6774.
[16] M. Wu, Y. Ai, B. Zeng, F. Zhao, In situ solvothermal growth of metal-organic
frameworkionic liquid functionalized graphene nanocomposite for highly
ecient enrichment of chloramphenicol and thiamphenicol, J. Chromatogr.
A 1427 (2016) 17.
[17] M. Babazadeh, R.H. Khanmiri, J. Abolhasani, E. Ghorbani-Kalhor, A. Hassanpour,
Synthesis and application of a novel functionalized magnetic metal organic
framework sorbent for determination of heavy metal ions in sh samples, Bull.
Chem. Soc. Jpn. 88 (2015) 871879.
[18] E. Ghorbani-Kalhor, R. Hosseinzadeh-Khanmiri, M. Babazadeh, J. Abolhasani,
A. Hassanpour, Synthesis and application of a novel magnetic metal-organic
framework nanocomposite for determination of Cd, Pb, and Zn in baby food
samples, Can. J. Chem. 93 (2015) 518525.
[19] S. Lin, N. Gan, L. Qiao, J. Zhang, Y. Cao, Y. Chen, Magnetic metal-organic
frameworks coated stir bar sorptive extraction coupled with GCMS for
determination of polychlorinated biphenyls in sh samples, Talanta 144 (2015)
11391145.
[20] F. Maya, C. Palomino Cabello, J.M. Estela, V. Cerd, G. Turnes Palomino,
Automatic in-syringe dispersive microsolid phase extraction using magnetic
metalorganic frameworks, Anal. Chem. 87 (2015) 75457549.
[21] M. Babazadeh, R. Hosseinzadeh-Khanmiri, J. Abolhasani, E. Ghorbani-Kalhor,
A. Hassanpour, Solid phase extraction of heavy metal ions from agricultural
samples with the aid of a novel functionalized magnetic metalorganic
framework, RSC Adv. 5 (2015) 1988419892.
[22] Y. Wang, H. Chen, J. Tang, G. Ye, H. Ge, X. Hu, Preparation of magnetic metal
organic frameworks adsorbent modied with mercapto groups for the
extraction and analysis of lead in food samples by ame atomic absorption
spectrometry, Food Chem. 181 (2014) 191197.
[23] H. Lan, N. Gan, D. Pan, F. Hu, T. Li, N. Long, et al., Development of a novel
magnetic molecularly imprinted polymer coating using porous zeolite
imidazolate framework-8 coated magnetic iron oxide as carrier for automated
solid phase microextraction of estrogens in sh and pork samples,
J. Chromatogr. A 1365 (2014) 3544.
[24] Y. Wang, Y. Wu, H. Ge, H. Chen, G. Ye, X. Hu, Fabrication of metal-organic
frameworks and graphite oxide hybrid composites for solid-phase extraction
and preconcentration of luteolin, Talanta 122 (2014) 9196.
[25] M.R. Sohrabi, Z. Matbouie, A.A. Asgharinezhad, A. Dehghani, Solid phase
extraction of Cd(II) and Pb(II) using a magnetic metal-organic framework, and
their determination by FAAS, Microchim. Acta 180 (2013) 589597.
[26] S. Zhang, Z. Du, G. Li, Metal-organic framework-199/graphite oxide hybrid
composites coated solid-phase microextraction bers coupled with gas
chromatography for determination of organochlorine pesticides from
complicated samples, Talanta 115 (2013) 3239.
[27] J. Gonzlez-Slamo, A.V. Herrera-Herrera, C. Fanali, J. Hernndez-Borges,
Magnetic nanoparticles for solid-phase extraction, LC-GC, Europe 29 (2016)
180193.
[28] M. Wierucka, M. Biziuk, Application of magnetic nanoparticles for magnetic
solid-phase extraction in preparing biological, environmental and food
samples, Trends Anal. Chem.; TrAC 59 (2014) 5058.
[29] A.H. Lu, E.L. Salabas, F. Schth, Magnetic nanoparticles: synthesis, protection,
functionalization and application, Angew. Chem. Int. Ed. Engl. 46 (2007)
12221244.
[30] R. Karami-Osboo, R. Miri, K. Javidnia, M.H. Shojaee, F. Kobarfard, Extraction
and determination of sulfadiazine and sulfathiazole in milk using magnetic
solid phase extraction-HPLC-UV, Anal. Methods 7 (2015) 15861589.
[31] J. Zhang, J. Shao, P. Guo, Y. Huang, A simple and fast Fe 3 O 4 magnetic
nanoparticles-based dispersion solid phase extraction of sudan dyes from food
and water samples coupled with high performance liquid chromatography,
Anal. Methods 5 (2013) 25032510.
[32] R. Gao, X. Cui, Y. Hao, L. Zhang, D. Liu, Y. Tang, A highly-ecient imprinted
magnetic nanoparticle for selective separation and detection of 17-estradiol
in milk, Food Chem. 194 (2016) 10401047.
[33] S.S. Miao, M.S. Wu, H.G. Zuo, C. Jiang, S.F. Jin, Y.C. Lu, et al., Coreshell magnetic
molecularly imprinted polymers as sorbent for sulfonylurea herbicide residues,
J. Agric. Food Chem. 63 (2015) 36343645.
[34] F. Ning, H. Peng, L. Dong, Z. Zhang, J. Li, L. Chen, et al., Preparation and
characterization of superparamagnetic molecularly imprinted polymers for
selective adsorption and separation of vanillin in food samples, J. Agric. Food
Chem. 62 (2014) 1113811145.
[35] Y.-G. Zhao, L.-X. Zhou, S.-D. Pan, P.-P. Zhan, X.-H. Chen, M.-C. Jin, Fast
determination of 22 sulfonamides from chicken breast muscle using coreshell
nanoring amino-functionalized superparamagnetic molecularly imprinted
polymer followed by liquid chromatography-tandem mass spectrometry,
J. Chromatogr. A 1345 (2014) 1728.
[36] C. McCullum, P. Tchounwou, L.-S. Ding, X. Liao, Y.-M. Liu, Extraction of aatoxins
from liquid foodstuff samples with polydopamine-coated superparamagnetic
nanoparticles for HPLCMS/MS analysis, J. Agric. Food Chem. 62 (2014)
42614267.
[37] H.-B. Zheng, J.-Z. Mo, Y. Zhang, Q. Gao, J. Ding, Q.-W. Yu, et al., Facile synthesis
of magnetic molecularly imprinted polymers and its application in magnetic
solid phase extraction for uoroquinolones in milk samples, J. Chromatogr.
A 1329 (2014) 1723.
[38] M. Karimi, F. Aboufazeli, H.R.L.Z. Zhad, O. Sadeghi, E. Naja, Determination
of sulfonamides in chicken meat by magnetic molecularly imprinted polymer
coupled to HPLC-UV, Food Anal. Method. 7 (2014) 7380.
[39] J. Li, H. Zhou, Y.-X. Liu, X.-Y. Yan, Y.-P. Xu, S.-M. Liu, Magnetic metal-organic
frameworks coated stir bar sorptive extraction coupled with GCMS for
determination of polychlorinated biphenyls in sh samples, Food Addit.
Contam. Part A Chem. Anal. Control Expo. Risk Assess. 31 (2014) 11391146.
[40] E. Naja, F. Aboufazeli, H.R.L.Z. Zhad, O. Sadeghi, V. Amani, A novel magnetic
ion imprinted nano-polymer for selective separation and determination of low
levels of mercury(II) ions in sh samples, Food Chem. 141 (2013) 40404045.
[41] Y.-K. Lv, C.-X. Zhao, P. Li, D.-Y. He, Z.-R. Yang, H.-W. Sun, Preparation of
doxycycline-imprinted magnetic microspheres by inverse-emulsion suspension
polymerization for magnetic dispersion extraction of tetracyclines from milk
samples, J. Sep. Sci. 36 (2013) 26562663.
[42] J. Zhan, G. Fang, Z. Yan, M. Pan, C. Liu, S. Wang, Preparation of a semicovalent,
molecularly surface imprinted polymer for the rapid determination of trace
acid orange II in food and environmental samples, Anal. Bioanal. Chem. 405
(2013) 63536363.
[43] Q. Zhao, Q. Lu, Y.-Q. Feng, Dispersive microextraction based on magnetic
polypyrrole nanowires for the fast determination of pesticide residues in
beverage and environmental water samples, Anal. Bioanal. Chem. 405 (2013)
47654776.
[44] R. Wang, Y. Wang, C. Xue, T. Wen, J. Wu, J. Hong, et al., Selective separation
and enrichment of glibenclamide in health foods using surface molecularly
imprinted polymers prepared via dendritic grafting of magnetic nanoparticles,
J. Sep. Sci. 36 (2013) 10151021.
[45] D. Chen, J. Deng, J. Liang, J. Xie, K. Huang, C. Hu, Coreshell magnetic
nanoparticles with surface imprinted polymer coating as a new adsorbent for
solid phase extraction of metronidazole, Anal. Methods 5 (2013) 722728.
[46] R. Gao, J. Zhang, X. He, L. Chen, Y. Zhang, Selective extraction of sulfonamides
from food by use of silica-coated molecularly imprinted polymer nanospheres,
Anal. Bioanal. Chem. 398 (2010) 451461.
[47] J. Chen, X. Zhu, Magnetic solid phase extraction using ionic liquid-coated
coreshell magnetic nanoparticles followed by high-performance liquid
chromatography for determination of rhodamine B in food samples, Food
Chem. 200 (2016) 1015.
[48] J. Chen, X. Zhu, Ionic liquid coated magnetic core/shell Fe 3 O 4 @SiO 2
nanoparticles for the separation/analysis of linuron in food samples,
Spectrochim. Acta [A.] 137 (2015) 456462.
[49] X. Zheng, L. He, Y. Duan, X. Jiang, G. Xiang, W. Zhao, et al., Poly(ionic liquid)
immobilized magnetic nanoparticles as new adsorbent for extraction and
enrichment of organophosphorus pesticides from tea drinks, J. Chromatogr.
A 1358 (2014) 3945.
[50] M.D. Farahani, F. Shemirani, Mixed hemi-micelle solid-phase extraction based
on modied magnetic nanoparticles for extraction of cadmium and lead from
food and water samples, J. AOAC Int. 97 (2014) 16821688.
[51] S.R. Yazdinezhad, A. Ballesteros-Gmez, L. Lunar, S. Rubio, Single-step
extraction and cleanup of bisphenol A in soft drinks by hemimicellar magnetic
solid phase extraction prior to liquid chromatography/tandem mass
spectrometry, Anal. Chim. Acta 778 (2013) 3137.
[52] H. Sun, Q.-W. Yu, H.-B. He, Q. Lu, Z.-G. Shi, Y.-Q. Feng, Nickel oxide
nanoparticle-deposited silica composite solid-phase extraction
for benzimidazole residue analysis in milk and eggs by liquid
chromatographymass spectrometry, J. Agric. Food Chem. 64 (2016) 356
363.
[53] S. zdemir, E. Kilin, V. Okumu, A. Poli, B. Nicolaus, I. Romano, Thermophilic
Geobacillus galactosidasius sp. nov. loaded -Fe2O3 magnetic nanoparticle for
the preconcentrations of Pb and Cd, Bioresour. Technol. 201 (2016) 269275.
[54] A. Mirabi, Z. Dalirandeh, A.S. Rad, Preparation of modied magnetic
nanoparticles as a sorbent for the preconcentration and determination of
cadmium ions in food and environmental water samples prior to ame atomic
absorption spectrometry, J. Magn. Magn. Mater. 381 (2015) 138144.
[55] S. Hassanpoor, G. Khayatian, A.R.J. Azar, Ultra-trace determination of arsenic
species in environmental waters, food and biological samples using a modied
aluminum oxide nanoparticle sorbent and AAS detection after multivariate
optimization, Microchim. Acta 182 (2015) 19571965.
 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
[56] C. Liu, C. Lu, Z. Tang, X. Chen, G. Wang, F. Sun, Aptamer-functionalized magnetic
nanoparticles for simultaneous uorometric determination of oxytetracycline
and kanamycin, Microchim. Acta 182 (2015) 25672575.
[57] Z. Taherimaslak, M. Amoli-Diva, M. Allahyari, K. Pourghazi, M.H. Mana, Low
density solvent based dispersive liquidliquid microextraction followed by
vortex-assisted magnetic nanoparticle based solid-phase extraction and
surfactant enhanced spectrouorimetric detection for the determination of
aatoxins in pistachio nuts, RSC Adv. 5 (2015) 1274712754.
[58] H. Abdolmohammad-Zadeh, Z. Talleb, Magnetite-doped eggshell membrane
as a magnetic sorbent for extraction of aluminium (III) ions prior to their
uorometric determination, Microchim. Acta 181 (2014) 17971805.
[59] M. Karimi, F. Aboufazelo, H.R.L.Z. Zhad, O. Sadeghi, E. Naja, Use of dipyridile
amine functionalized magnetic nanoparticles for preconcentration
and determination of lead ions in food samples, J. AOAC Int. 97 (2014)
14461451.
[60] M. Hashemi, Z. Taherimaslak, S. Rashidi, Enhanced spectrouorimetric
determination of aatoxin M1 in liquid milk after magnetic solid phase
extraction, Spectrochim. Acta [A.] 128 (2014) 583590.
[61] A.A. Asgharinezhad, H. Ebrahimzadeh, M. Rezvani, N. Shekari, M. Loni, A novel
4-(2-pyridylazo) resorcinol functionalised magnetic nanosorbent for selective
extraction of Cu(II) and Pb(II) ions from food and water samples, Food Addit.
Contam. Part A Chem. Anal. Control Expo. Risk Assess. 31 (2014) 11961204.
[62] N. Sehati, N. Dalali, S. Soltanpour, M.S.S. Dorraji, Extraction and
preconcentration of tylosin from milk samples through functionalized TiO2
nanoparticles reinforced with a hollow ber membrane as a novel solid/liquid-
phase microextraction technique, J. Sep. Sci. 37 (2014) 20252031.
[63] M.-E.S. Synaridou, V.A. Sakkas, C.D. Stalikas, T.A. Albanis, Evaluation of magnetic
nanoparticles to serve as solid-phase extraction sorbents for the determination
of endocrine disruptors in milk samples by gas chromatography mass
spectrometry, J. Chromatogr. A 1348 (2014) 7179.
[64] M. Bayat, F. Shemirani, M.H. Beyki, Utilization of facile synthesized Fe3O4
nanoparticles as a selective support for preconcentration of lead ions from
food and environmental samples, Anal. Methods 6 (2014) 53455352.
[65] M.. Molina-Delgado, M.P. Aguilar-Caballos, A. Gomez-Hens, Determination
of soy proteins in food samples by dispersive solid-phase immunoextraction
and dynamic long-wavelength uorometry, Microchim. Acta 180 (2013)
12791286.
[66] H. Zhang, Q.-S. Liu, C.-L. Yang, J.-Z. Ly, L.-Q. Xie, M.-J. Tang, et al., C18/C8-
functionalized magnetic silica nanospheres (Fe3O4@Si-C8/C18) as capture probes
for highly ecient and rapid purication of veterinary drug residues, Food
Anal. Method. 6 (2013) 933940.
[67] L.-S. Qing, Y. Xue, Y.-M. Liu, J. Liang, J. Xie, X. Liao, Rapid magnetic solid-phase
extraction for the selective determination of isoavones in soymilk using
baicalin-functionalized magnetic nanoparticles, J. Agric. Food Chem. 61 (2013)
80728078.
[68] F. Wei, Q. Zhao, X. Lv, X.-Y. Dong, Y.-Q. Feng, H. Chen, Rapid magnetic solid-
phase extraction based on monodisperse magnetic single-crystal ferrite
nanoparticles for the determination of free fatty acid content in edible oils,
J. Agric. Food Chem. 61 (2013) 7683.
[69] X. Wu, J. Hu, B. Zhu, L. Lu, X. Huang, D. Pang, Aptamer-targeted magnetic
nanospheres as a solid-phase extraction sorbent for determination of
ochratoxin A in food samples, J. Chromatogr. A 1218 (2011) 73417346.
[70] A. Kaur, U. Gupta, Application of 1-(2-Pyridylazo)-2-naphthol anchored SiO2
nanoparticles for the preconcentration of trace Pb2+ from different water and
food samples, Chinese J. Chem. 27 (2009) 18331838.
[71] S. Iijima, Helical microtubules of graphitic carbon, Nature 354 (1991) 5658.
[72] A.V. Herrera-Herrera, M.. Gonzlez-Curbelo, J. Hernndez-Borges, M..
Rodrguez-Delgado, Carbon nanotubes applications in separation science: a
review, Anal. Chim. Acta 734 (2012) 130.
[73] B. Socas-Rodrguez, A.V. Herrera-Herrera, M. Asensio-Ramos, J.
Hernndez-Borges, Recent applications of carbon nanotube sorbents in
analytical chemistry, J. Chromatogr. A 1357 (2014) 110146.
[74] L.M. Ravelo-Prez, A.V. Herrera-Herrera, J. Hernndez-Borges, M..
Rodrguez-Delgado, Carbon nanotubes: solid-phase extraction, J. Chromatogr.
A 1217 (2010) 26182641.
[75] X. Xu, N. Long, J. Lv, L. Wang, M. Zhang, X. Qi, et al., Functionalized multiwalled
carbon nanotube as dispersive solid-phase extraction materials combined with
high-performance liquid chromatography for thiabendazole analysis in
environmental and food samples, Food Anal. Method. 9 (2016) 3037.
[76] X. Xu, M. Zhang, L. Wang, S. Zhang, M. Liu, N. Long, et al., Determination of
rhodamine b in food using ionic liquidcoated multiwalled carbon nanotube
based ultrasound-assisted dispersive solid-phase microextraction followed by
high-performance liquid chromatography, Food Anal. Method. 9 (2016)
16961705.
[77] A.Y. Badjah Hadj Ahmed, S.M. Wabaidur, M.R. Siddiqui, Z.A. Alothman, M.S.
Obeid, M.R. Khan, et al., Simultaneous determination of twenty-ve
polyphenols in multioral and cactus honeys using solid-phase extraction and
high-performance liquid chromatography with photodiode array detection,
Eur. Food Res. Technol. 242 (2016) 943952.
[78] S.M. Wabaidur, Y.B.H. Ahmed, Z.A. Alothman, M.S. Obbed, N.M. AL-Harbi, T.M.
AL-Turki, Ultra high performance liquid chromatography with mass
spectrometry method for the simultaneous determination of phenolic
constituents in honey from various oral sources using multiwalled carbon
nanotubes as extraction sorbents, J. Sep. Sci. 28 (2015) 25972606.
[79] D. Chen, Y.-Q. Huang, X.-M. He, Z.-G. Shi, Y.-Q. Feng, Coupling carbon nanotube
lm microextraction with desorption corona beam ionization for rapid analysis
219
of Sudan dyes (IIV) and rhodamine B in chilli oil, Analyst 140 (2015)
17311738.
[80] A. Ghiasvand, S. Dowlatshah, N. Nouraei, N. Heidari, F. Yazdankhah, A solid-
phase microextraction platinized stainless steel ber coated with a multiwalled
carbon nanotube-polyaniline nanocomposite lm for the extraction of thymol
and carvacrol in medicinal plants and honey, J. Chromatogr. A 1406 (2015)
8793.
[81] Y.-L. Wu, R.-X. Chen, Y. Zhu, J. Zhao, T. Yang, Simultaneous determination of
sixteen amide fungicides in vegetables and fruits by dispersive solid phase
extraction and liquid chromatographytandem mass spectrometry,
J. Chromatogr. B 989 (2015) 1120.
[82] L. Zeng, X. Wu, Y. Li, D. Lu, C. Sun, Multiwalled carbon nanotube-dispersive
solid phase extraction followed by high performance capillary electrophoresis
for simultaneous determination of six adulterants in antihypertensive
functional foods, Anal. Methods 7 (2015) 543550.
[83] H. Zhao, N. Li, J. Li, X. Qiao, Z. Xu, Preparation and application of chitosan-
grafted multiwalled carbon nanotubes in matrix solid-phase dispersion
extraction for determination of trace acrylamide in foods through high-
performance liquid chromatography, Food Anal. Method. 8 (2015) 13631371.
[84] E. Ghorbani-Kalhor, M. Behbahani, J. Abolhasani, R. Hosseinzadeh-Khanmiri,
Synthesis and characterization of modied multiwall carbon nanotubes with
poly (N-phenylethanolamine) and their application for removal and trace
detection of lead ions in food and environmental samples, Food Anal. Method.
8 (2015) 13261334.
[85] A.Y. Badjah Hadj Ahmed, M.S. Obbed, S.M. Wabaidur, Z.A. Al-Othman, N.H.
Al-Shaalan, High-performance liquid chromatography analysis of phenolic acid,
avonoid, and phenol contents in various natural yemeni honeys using
multi-walled carbon nanotubes as a solid-phase extraction adsorbent, J. Agric.
Food Chem. 62 (2014) 54435450.
[86] J.A. Sweileh, K.Y. Misef, A.H. El-Sheikh, M.S. Sunjuk, Development of a new
method for determination of aluminum (Al) in Jordanian foods and drinks:
solid phase extraction and adsorption of Al3+-D-mannitol on carbon nanotubes,
J. Food Comp. Anal. 33 (2014) 613.
[87] M. Rezvani, H. Ebrahimzadeh, A. Aliakbari, A. Khalilzadeh, M. Kasaeian, M.M.
Amini, Novel modied carbon nanotubes as a selective sorbent for
preconcentration and determination of trace copper ions in fruit samples,
J. Sep. Sci. 37 (2014) 25592565.
[88] F. Aboufazeli, H.R.L.Z. Zhad, O. Sadeghi, M. Karimi, E. Naja, Novel Cd(II) ion
imprinted polymer coated on multiwall carbon nanotubes as a highly selective
sorbent for cadmium determination in food samples, J. AOAC Int. 97 (2014)
173178.
[89] V. Prez-Fernndez, A. Gentili, A. Martinelli, F. Caretti, R. Curini, Evaluation
of ixidized buckypaper as material for the solid phase extraction of cobalamins
from milk: its ecacy as individual and support sorbent of a hydrophilic-
lipophilic balance copolymer, J. Chromatogr. A 1428 (2016) 255266.
[90] Y. Zhao, C. Bi, X. He, L. Chen, Y. Zhang, Preparation of molecularly imprinted
polymers based on magnetic carbon nanotubes for determination of
sulfamethoxazole in food samples, RSC Adv. 5 (2015) 7030970318.
[91] F. Makkliang, P. Kanatharana, P. Thavarungkul, C. Thammakhet, Development
of magnetic micro-solid phase extraction for analysis of phthalate esters in
packaged food, Food Chem. 166 (2015) 275282.
[92] G.D. Tarigh, F. Shemirani, Simultaneous insitu derivatization and ultrasound-
assisted dispersive magnetic solid phase extraction for thiamine determination
by spectrouorimetry, Talanta 123 (2014) 7177.
[93] X. Du, S. Lin, N. Gan, X. Chen, Y. Cao, T. Li, et al., Multi-walled carbon nanotube
modied dummy-template magnetic molecularly imprinted microspheres as
solid-phase extraction material for the determination of polychlorinated
biphenyls in sh, J. Sep. Sci. 37 (2014) 15911600.
[94] Z. Eshaghi, M.A.-K. Khooni, T. Heidari, Determination of brilliant green from
sh pond water using carbon nanotube assisted pseudo-stir bar solid/liquid
microextraction combined with UVvis spectroscopydiode array detection,
Spectrochim. Acta [A.] 79 (2011) 603607.
[95] Y. Qu, C. Liu, F. Luo, B. Qiu, X. Chen, Electropolymerization of single-walled
carbon nanotubes composited with polypyrrole as a solid-phase
microextraction ber for the detection of acrylamide in food samples using
GC with electron-capture detection, J. Sep. Sci. 36 (2013) 38893895.
[96] B. Socas-Rodrguez, A.V. Herrera-Herrera, M. Asensio-Ramos, J.
Hernndez-Borges, Dispersive solid-phase extraction, in: J.L. Anderson, A.
Berthod, V. Pino Estvez, A.M. Stalcup (Editors), Analytical Separation Science,
E-Wiley-VCH, Weinheim, 2015, pp. 15251569.
[97] B. Bingol, M. Kulcu, Optimization of the solid phase extraction method for
determination of Cu(II) in natural waters by using response surface
methodology, Analyst 136 (2011) 40364044.
[98] R. Sitko, B. Zawisza, E. Malicka, Modication of carbon nanotubes for
preconcentration, separation and determination of trace-metal ions, Trends
Anal. Chem.; TrAC 37 (2012) 2231.
[99] C. Yu, Y. Li, Q. Zhang, N. Zou, K. Gu, X. Li, et al., Decrease of pirimiphos-methyl
and deltamethrin residues in stored rice with post-harvest treatment, Int. J.
Environ. Res. Public Health 11 (2014) 53725381.
[100] X. Hou, S. Lei, S. Qiu, L. Guo, S. Yi, W. Liu, A multi-residue method for the
determination of pesticides in tea using multi-walled carbon nanotubes
as a dispersive solid phase extraction absorbent, Food Chem. 153 (2014)
121129.
[101] Y. Qin, P. Zhao, S. Fan, Y. Han, Y. Li, N. Zou, et al., The comparison of dispersive
solid phase extraction and multi-plug ltration cleanup method based on
multi-walled carbon nanotubes for pesticides multi-residue analysis by liquid
220 J. Gonzlez-Slamo et al. / Trends in Analytical Chemistry 85 (2016) 203220
chromatography tandem mass spectrometry, J. Chromatogr. A 1385 (2015)
111.
[102] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos,
et al., Electric eld effect in atomically thin carbon lms, Science 306 (2004)
666669.
[103] Z. Huang, H.K. Lee, Materials-based approaches to minimizing solvent usage
in analytical sample preparation, Trends Anal. Chem.; TrAC 39 (2012) 228244.
[104] R. Sitko, B. Zawisza, E. Malicka, Graphene as a new sorbent in analytical
chemistry, Trends Anal. Chem.; TrAC 51 (2013) 3343.
[105] V. Chabot, D. Higgins, A. Yu, X. Xiao, Z. Chen, J. Zhang, A review of graphene
and graphene oxide sponge: material synthesis and applications to energy
and the environment, Energy Environ. Sci. 7 (2014) 15641596.
[106] C. Li, G. Shi, Three-dimensional graphene architectures, Nanoscale 4 (2012)
55495563.
[107] W.S. Hummers Jr., R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem.
Soc. 80 (1958) 1339.
[108] L. Yu, P. Li, Q. Zhang, W. Zhang, X. Ding, X. Wang, Graphene oxide: an adsorbent
for the extraction and quantication of aatoxins in peanuts by high-
performance liquid chromatography, J. Chromatogr. A 1318 (2013) 2734.
[109] B. Ebrahimi, S. Bahar, S.E. Moedi, Evaluation of graphene as a solid-phase
extraction sorbent for the preconcentration and determination of trace
amounts of nickel in food samples prior to ame atomic absorption
spectrometry, J. AOAC Int. 98 (2015) 822827.
[110] H. Zhai, Z. Su, Z. Chen, Z. Liu, K. Yuan, L. Huang, Molecularly imprinted coated
graphene oxide solid-phase extraction monolithic capillary column for selective
extraction and sensitive determination of phloxine B in coffee bean, Anal. Chim.
Acta 865 (2015) 1621.
[111] Q. Zhang, G. Li, X. Xiao, Acrylamide-modied graphene for online micro-solid-
phase extraction coupled to high-performance liquid chromatography for
sensitive analysis of heterocyclic amines in food samples, Talanta 131 (2015)
127135.
[112] S.-S. Hu, W. Cao, J.-H. Da, H.-B. Dai, J. Cao, L.-H. Ye, et al., Dispersive micro
solid-phase extraction with graphene oxide for the determination of phenolic
compounds in dietary supplements by ultra-high performance liquid
chromatography coupled with quadrupole time-of-ight tandem mass
spectrometry, Food Anal. Method. 8 (2015) 833840.
[113] L. Min, P. Quing-quing, C. Yu-feng, T. Qian, F. Qing, A rapid space-resolved
solid-phase microextraction method as a powerful tool to determine
contaminants in wine based on their volatility, Food Chem. 176 (2015) 1216.
[114] A. Islam, H. Ahmad, N. Zaidi, S. Kumar, Graphene oxide sheets immobilized
polystyrene for column preconcentration and sensitive determination of lead
by ame atomic absorption spectrometry, ACS Appl. Mater. Interfaces 6 (2014)
1325713265.
[115] M. Sun, P. Cui, S. Ji, R. Tang, Q. Wu, C. Wang, et al., Octadecyl-modied graphene
as an adsorbent for hollow ber liquid phase microextraction of chlorophenols
from honey, Bull. Korean Chem. Soc. 35 (2014) 10111015.
[116] M. Behbahani, N.A.G. Tapeh, M. Mahyari, A.R. Pourali, B.G. Amin, A. Shaabani,
Monitoring of trace amounts of heavy metals in different food and water
samples by ame atomic absorption spectrophotometer after preconcentration
by amine-functionalized graphene nanosheet, Environ. Monit. Assess. 186
(2014) 72457257.
[117] C. Zhang, Z. Zhanga, G. Li, Preparation of sulfonated graphene/polypyrrole
solid-phase microextraction coating by in situ electrochemical polymerization
for analysis of trace terpenes, J. Chromatogr. A 1346 (2014) 815.
[118] R. Qi, H. Jiang, S. Liua, Q. Jia, Preconcentration and determination of pesticides
with graphene-modied polymer monolith combined with high performance
liquid chromatography, Anal. Methods 6 (2014) 14271434.
[119] M. Karimi, F. Aboufazeli, H.R.L.Z. Zhad, Cadmium ions determination in sea
food samples using dipyridyl-functionalized graphene nano-sheet, Food Anal.
Method. 7 (2014) 669675.
[120] M.R. Pourjavid, A.A. Sehat, M. Arabieh, S.R. Youse, M.H. Hosseini, M. Rezaee,
Column solid phase extraction and ame atomic absorption spectrometric
determination of manganese(II) and iron(III) ions in water, food and biological
samples using 3-(1-methyl-1H-pyrrol-2-yl)-1H-pyrazole-5-carboxylic acid on
synthesized graphene oxide, Mater. Sci. Eng. C Mater. Biol. Appl. 35 (2014)
370378.
[121] O. Sayar, K. Mehrani, F. Hoseinzadeh, A. Mehrani, O. Sadeghi, Comparison of
the performance of different modied graphene oxide nanosheets for the
extraction of Pb(II) and Cd(II) from natural samples, Microchim. Acta 181
(2014) 313320.
[122] W. Zhang, Z. Zhang, J. Zhang, J. Meng, T. Bao, Z. Chen, Covalent immobilization
of graphene onto stainless steel wire for jacket-free stir bar sorptive extraction,
J. Chromatogr. A 1351 (2014) 1220.
[123] L. Chen, T. Zhou, Y. Zhang, Y. Lu, Rapid determination of trace sulfonamides
in sh by graphene-based SPE coupled with UPLC/MS/MS, Anal. Methods 5
(2013) 43634370.
[124] L. Chen, Y. Lu, S. Li, X. Lin, Z. Xu, Z. Dai, Application of graphene-based
solid-phase extraction for ultra-fast determination of malachite green and its
metabolite in sh tissues, Food Chem. 141 (2013) 13831389.
[125] J. Wu, L. Chen, P. Mao, Y. Lu, H. Wang, Determination of chloramphenicol in
aquatic products by graphene-based SPE coupled with HPLC-MS/MS, J. Sep.
Sci. 35 (2012) 35863592.
[126] M. Khan, E. Yilmaz, B. Sevinc, E. Sahmetlioglu, J. Shah, M.R. Jan, et al.,
Preparation and characterization of magnetic allylamine modied graphene
oxide-poly(vinyl acetate-co-divinylbenzene) nanocomposite for vortex assisted
magnetic solid phase extraction of some metal ions, Talanta 146 (2016)
130137.
[127] S. Mahpishanian, H. Sereshti, M. Baghdadiba, Superparamagnetic coreshells
anchored onto graphene oxide grafted with phenylethyl amine as a nano-
adsorbent for extraction and enrichment of organophosphorus pesticides from
fruit, vegetable and water samples, J. Chromatogr. A 1406 (2015) 4858.
[128] X. Wang, N. Chen, Q. Han, Z. Yang, J. Wu, C. Xue, et al., Selective separation
and determination of the synthetic colorants in beverages by magnetic
solid-phase dispersion extraction based on a Fe3O4/reduced graphene oxide
nanocomposite followed by high-performance liquid chromatography with
diode array detection, J. Sep. Sci. 38 (2015) 21672173.
[129] S. Lin, N. Gan, J. Zhang, X. Chen, Y. Cao, T. Li, A novel reductive graphene
oxide-based magnetic molecularly imprinted poly (ethylene-co-vinyl alcohol)
polymers for the enrichment and determination of polychlorinated biphenyls
in sh samples, J. Mol. Recognit. 28 (2015) 359368.
[130] S. Bahar, F. Karami, Amino-functionalized Fe 3 O 4 graphene oxide
nanocomposite as magnetic solid-phase extraction adsorbent combined with
ame atomic absorption spectrometry for copper analysis in food samples,
J. Iran Chem. Soc. 12 (2015) 22132220.
[131] X. Liu, X. Zhou, C. Wang, Q. Wu, Z. Wang, Magnetic three-dimensional graphene
solid-phase extraction of chlorophenols from honey samples, Food Addit.
Contam. Part A Chem. Anal. Control Expo. Risk Assess. 32 (2015) 4047.
[132] Z. Eshaghi, H.R. Beheshti, J. Feizy, Extraction of aatoxins from food samples
using graphene-based magnetic nanosorbents followed by high-performance
liquid chromatography: a simple solution to overcome the problems of
immunoanity columns, J. Sep. Sci. 37 (2014) 25662573.
[133] F. Ning, H. Peng, J. Li, L. Chen, H. Xi, Molecularly imprinted polymer on magnetic
graphene oxide for fast and selective extraction of 17-estradiol, J. Agric. Food
Chem. 62 (2014) 74367443.
[134] E. Yavuz, S. Tokaloglu, H. Sxahan, S. Patat, A graphene/Co3O4 nanocomposite
as a new adsorbent for solid phase extraction of Pb(II), Cu(II) and Fe(III) ions
in various samples, RSC Adv. 3 (2013) 2465024657.
[135] M. Hou, X. Zhang, C. Wang, Z. Wang, The use of silica-coated magnetic
graphene microspheres as the adsorbent for the extraction of pyrethroid
pesticides from orange and lettuce samples followed by GCMS analysis,
J. Sep. Sci. 36 (2013) 32423248.
[136] N. Gan, J. Zhou, P. Xiong, F. Hu, Y. Cao, T. Li, et al., An ultrasensitive
electrochemiluminescent immunoassay for aatoxin M1 in milk, based on
extraction by magnetic graphene and detection by antibody-labeled CdTe
quantumn dots-carbon nanotubes nanocomposite, Toxins (Basel) 5 (2013)
865883.
[137] L. Gao, L. Chen, Preparation of magnetic carbon nanotubes for separation of
pyrethroids from tea samples, Microchim. Acta 180 (2013) 423430.
[138] D. Xiao, P. Dramou, N. Xiong, H. He, D. Yuan, H. Dai, et al., Preparation of
molecularly imprinted polymers on the surface of magnetic carbon nanotubes
with a pseudo template for rapid simultaneous extraction of four
uoroquinolones in egg samples, Analyst 138 (2013) 32873296.