Trends in Analytical Chemistry 178 (2024) 117826

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Trends in Analytical Chemistry

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Advanced materials for magnetic solid-phase extraction of mycotoxins:

A review
Ana Castell , Natalia Arroyo-Manzanares , Pilar Viñas , Ignacio López-García , Natalia Campillo *
Department of Analytical Chemistry, Faculty of Chemistry, Regional Campus of International Excellence “Campus Mare Nostrum", University of Murcia, E-30100,
Murcia, Spain

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

Keywords: Mycotoxins can occur at various stages of the food production process. Due to the toxicity of many of these
Mycotoxins compounds for human health, the development of analytical methodologies that allow their detection and
Magnetic solid-phase extraction remediation in food is of great interest. However, food analysis is challenging due to the complexity of the
Molecularly imprinted polymer
matrices, so sample treatment is a crucial step. Magnetic solid-phase extraction (MSPE) has become one of the
Metal-organic framework
Covalent organic framework
most popular green approaches for the isolation of mycotoxins from complex matrices. Furthermore, advanced
Sample treatment magnetic materials as molecularly imprinted polymers, metal-organic frameworks and covalent organic frame­
Food analysis works have emerged as promising candidates for MSPE, as they offer a simple and efficient application for
mycotoxin extraction due to the possibility to modify and functionalize their surface according to specific re­
quirements. This review provides an overview of the synthesis and recent applications of these sorbents for the
MSPE isolation of mycotoxins from complex matrices.

1. Introduction Food Safety Authority (EFSA) and the Codex Alimentarius Commission
(CAC) [1].
Food safety is one of the main issues of global concern. Contamina­ Due to the importance of ensuring food safety from mycotoxin
tion of food with toxic substances as mycotoxins is a major contributor occurrence, reliable and efficient analytical methods are required. In
to food safety problems [1]. These compounds are almost inevitably addition, analysis of food samples is challenging due to the complexity
produced by several species of fungi such as Penicillium, Fusarium, of the matrices, which makes selective extraction of target analytes a
Aspergillus or Alternaria, mainly in agricultural products. Mycotoxin very difficult task. Sample preparation is therefore a crucial step in food
contamination of food can occur at any stage of the food production analysis to achieve efficient isolation and/or preconcentration of ana­
process and is favoured under conditions of high humidity and tem­ lytes and remove matrix interferences prior to instrumental analysis [3].
perature [1,2]. Over 400 different mycotoxins have been identified, the Current trends in sample preparation are based on extraction techniques
most common found in food being aflatoxins (AFs) (G1, G2, B1, B2 and following the principles of Green Analytical Chemistry, with minimal
M1), zearalenone (ZEN), patulin (PAT), ochratoxins (OTs) (A, B and C), sample and solvent consumption, reduction of waste generation and few
T-2 and HT-2 toxin, fumonisins (Fs) (B1 and B2), nivalenol (NIV) and treatment steps [4].
deoxynivalenol (DON) [3]. Solid phase extraction (SPE) is a highly versatile sample preparation
The consumption of food contaminated with mycotoxins can cause technique for the extraction and preconcentration of target analytes
alterations in the organism and serious diseases that pose a threat to based on the adsorption on a solid sorbent. Therefore, the extraction
health. Moreover, the co-occurrence of multiple mycotoxins in foods is efficiency depends on the chemical properties of the analyte, its affinity
very frequent, which can lead to additive or synergistic effects with for the sorbent and the nature of the sample matrix. Traditional SPE
greater toxic effects than the individual toxins. Consequently, limit columns were widely used for the isolation of mycotoxins. However, the
values and detection requirements for mycotoxins have been jointly limited chemical and physical stability at high or low pH, low capacity
established by the World Health Organization (WHO), the Food and and restricted reusability of the extraction sorbents limit the use of this
Agriculture Organization of the United Nations (FAO), the European technique [4]. Immunoaffinity columns (IACs) and aptamer affinity

* Corresponding author.
E-mail address: [email protected] (N. Campillo).

https://doi.org/10.1016/j.trac.2024.117826
Received 17 March 2024; Received in revised form 28 May 2024; Accepted 18 June 2024
Available online 20 June 2024
0165-9936/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
A. Castell et al. Trends in Analytical Chemistry 178 (2024) 117826

columns (AACs) have also been applied for the analysis of mycotoxins, in this field [11]. Focusing on miniaturized techniques, Pochivalov et al.
offering greater specificity and sensitivity. Commercial IACs have been reported the application of solid-phase and liquid-phase microextraction
mainly used for the analysis of OTs, AFs, trichothecenes or Fs while the methods for mycotoxin analysis [12]. Reviews based on the use of
application of AAC is limited to the isolation and preconcentration of nanomaterials in SPE have also been reported [1,5,13]. Chen and
OTA, ZEN, AFs and Fs, due to the limited aptamer sequence available. Inbaraj focused on the use of carbon nanomaterials as sorbents [14].
Some of the limitations of IAC are susceptibility to the sample matrix, This review provides an overview of recent synthesis and applications of
high cost, cross-reactivity of antibodies, poor tolerance to organic sol­ magnetic materials as sorbents for the extraction and preconcentration
vents, and difficulty in acquisition [5]. SPE has evolved significantly, of mycotoxins from different matrices, focused on the use of MIPs,
resulting in miniaturized methodologies, such as solid phase micro­ metal-organic frameworks (MOFs) and covalent organic frameworks
extraction (SPME), stir bar sorptive extraction (SBSE), dispersive solid (COFs) for MSPE. The popularity of these materials has increased in
phase extraction (d-SPE) and magnetic solid-phase extraction (MSPE), recent years due to their benefits in detecting and monitoring food
which allow the use of small amounts of extractant and sorbent. Thus, contaminants such as mycotoxins.
the development of materials science and nanotechnology has led to the
exploration of novel nanoscale materials for the isolation of various 2. Discussion
compounds of interest. Since 2009, nanomaterials have been used for
the isolation of mycotoxins in food, both for quantification and reme­ 2.1. Nanomaterials for mycotoxin analysis by MSPE
diation purposes [6]. Due to their extremely small size, unique structure,
functional properties and high surface area, they are powerful sorbents Nowadays, MSPE has emerged as a promising approach for rapid,
that enable fast, efficient and environmentally friendly compound sustainable, high-throughput preconcentration and removal of con­
isolation [7,8]. In particular, the synthesis of magnetic nanomaterials taminants from complex matrices [4]. The popularity of this technique is
with specific properties has attracted the interest of researchers. In largely due to advances in magnetic sorbents, which in recent years have
addition to their easy separation by means of an external magnetic field, demonstrated exceptional adsorption abilities. Magnetic sorbents are
which avoids steps such as filtration or centrifugation, they have good usually composed of magnetic nanoparticles (MNPs) and modified
dispersibility in solvents and the possibility of modifying and function­ functional components, which play a dominant role in MSPE technology
alizing their surface to improve specificity or adsorption efficiency. and directly affect the extraction efficiency and selectivity [15]. Fig. 1
Moreover, these materials have a high reusability rate. Magnetic mate­ shows the typical MSPE procedure for the extraction of analytes.
rials derived from iron, cobalt or nickel are the most widely used. In Magnetic sorbents require good chemical stability, high dis­
particular, Fe3O4 (magnetite) as a magnetic core is widely used due to its persibility and high affinity to ensure the efficiency and reproducibility
chemical stability, biocompatibility, high magnetic moments and rela­ of the purification process. Therefore, MSPE sorbents are usually
tive ease of preparation [7]. designed as core-shell structures, where the magnetic core surface is
Recently, several reviews have been published on mycotoxin analysis functionalized to form a specific recognition layer with high affinity for
based on SPE. Bian et al. covered the different sample pretreatment the targets. The preparation of these sorbents involves several complex
methods used for the determination of mycotoxins in foods based on SPE steps that can result in significant batch-to-batch variability, which to
and liquid-liquid extraction (LLE) approaches, as well as their minia­ some extent limit the widespread use of these materials. In addition, the
turized versions [9]. Cavalera et al. discussed the use of molecularly magnetic properties may decrease after several modifications on the
imprinted polymers (MIPs) as sorbents for cleaning and preconcentra­ core surface of MNPs, which directly affects the adsorption and sepa­
tion of mycotoxins, describing different procedures reported by litera­ ration efficiency. Thus, it is important to develop magnetic SPE mate­
ture [10] and Cardoso et al. reviewed the use of MIPs for on-line sample rials with simple preparation, stable magnetic properties, and high
extraction in liquid chromatography and described recent applications affinity for target compounds [1]. The efficiency of magnetic

Fig. 1. General MSPE procedure for analyte extraction.

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A. Castell et al. Trends in Analytical Chemistry 178 (2024) 117826

nanomaterials is generally evaluated by parameters such as extraction materials are shown in Fig. S1.
recovery, matrix effect, detection and quantification limits, material
reusability, extraction time, and amount of sorbent material required.
Among these materials, MIPs, MOFs and COFs stand out as popular 2.2. Molecularly imprinted polymers (MIPs)
sorbents in mycotoxin isolation due to their high stability, reusability
and efficiency. Magnetic carbon nanotubes (MCNTs) [16], which are MIPs are synthetic polymers that mimic the biological mechanism of
nanomaterials with a large surface area and unique structure, along with natural receptors and allow the recognition of target molecules by
magnetic hyper-crosslinked polymers (MHCP) [17] have been used as binding them in specific cavities [50,51]. The synthesis of MIPs involves
sorbents for the extraction of mycotoxins from food. the presence of a template molecule of the target analyte and the
Although the use of magnetic sorbents generally results in lower polymerization of the functional monomers and crosslinkers. Bonding
power requirements and less sample and solvent consumption, the between the template and functional monomers can be established by
environmental sustainability of the proposed methods depends on the covalent, semi-covalent, and non-covalent bonds (electrostatic in­
sorbent, coating, and application. Therefore, it is important to consider teractions, van der Waals forces, π-π interactions or hydrogen bonding).
the complete life cycle of the sorbents, from production, through use, to Non-covalent synthesis techniques of MIPs are the most widely used due
disposal and recycling. The green synthesis of nanoparticles proposes to their relatively favorable conditions and fast elimination and
the use of green reagents or natural compounds such as microorganisms rebinding of the template [51]. Once the polymerization is complete, the
as an alternative to chemical products [18,19]. Among the green re­ template molecule is removed. The result is a three-dimensional
agents, the use of biopolymers, ascorbic acid and amino acids stands out network of highly cross-linked polymers with binding sites comple­
for the synthesis and stabilization of MNPs [19]. On the other hand, mentary to the analyte of interest in terms of functionality, size and
microorganisms such as fungi and bacteria can synthesize extracellular shape [52].
enzymes capable of producing relatively pure nanoparticles with low The preparation of MIPs for selective mycotoxin extraction is
toxicity and high biodegradability [18]. Certainly, plant extracts have considered more complex than for other target molecules. This is not due
proven to be very good best candidates for the synthesis of green to the lack of suitable functional groups to establish non-covalent in­
nanoparticles because the synthesis is fast, on a large scale, and produces teractions during the imprinting process, since the structure of myco­
more stable structures than microorganisms [20]. This sets a new stan­ toxins contains many groups suitable for hydrogen bonding or ion-pair
dard for highly sustainable and economically viable clean and green interactions, and there is also full chemical compatibility with the
technologies by enabling the synthesis of these nanomaterials without organic reagents used during the polymerization process (functional
significant environmental impact [19]. monomers, crosslinkers and radical initiators). The difficulty lies in the
The number of publications on the topic of mycotoxin determination danger of handling due to the toxicity of mycotoxins and the limited
by MSPE using MIPs, MOFs, and COFs as magnetic materials has availability of commercial standards. A crucial challenge lies in the
increased from 2016 to date (Fig. 2a). The first publication on MOFs incomplete removal of residual template from the polymer matrix,
about mycotoxin extraction by MSPE was in 2018 [21], and COFs which is gradually released during loading, washing and elution. This
started to be used in 2021 [22]. The application of MIPs was continu­ template loss is detected at trace levels during the elution step and is a
ously evolving from 2016 to date. Regarding the mycotoxins studied in major source of interference and systematic error. In addition, concerns
these publications, AFs [23–37] and ZEN and its derivatives [22,26, about potential sample contamination are one of the major obstacles. To
37–45] were the most abundant, due to their high prevalence in food overcome this drawback, it has been shown that the most successful
products. In addition, OTs have been also studied in a high percentage of strategy is the use of a mimic of the analyte as a template molecule [53].
the publications [21,25,26,29,38,46–48], especially OTA; while other These materials are in line with the concepts of green chemistry due
mycotoxins such as enniatins (ENNs) [29], fusarenon-X (FUS-X) [49], to their reusability, minimizing the generation of solid waste, and their
altenusin (ALS) and some Alternaria mycotoxins [38] have been less chemical and mechanical stability. However, the use of harmless or
studied (Fig. 2b). Recent publications describing the composition of environmentally friendly reagents during synthesis is crucial to develop
magnetic materials and the results obtained for the extraction of green MIPs, where user and environmental safety are prioritized.
different mycotoxins are summarized in this study. The molecular Although most of the reported work on MIPs is not completely green,
structures of the most studied mycotoxins using MIPs, MOFs, and COFs there has been steady progress in the direction of polymers synthesized
using environmentally friendly reagents [54].

Fig. 2. (a) Number of publications per year of MIPs, MOFs and COFs as magnetic materials for mycotoxin extraction based on MSPE; (b) Mycotoxins studied in the
publications, in percentage (AFs: aflatoxins; ALS: altenusin; ALT: altenuene; AME: alternariol methyl ether; AOH: alternariol; CIT: citrinin; COFs: covalent organic
frameworks; DAS: diacetoxyscirpenol; DON: deoxynivalenol; ENNs: enniatins; FUS-X: fusarenon-X; MIPs: molecularly imprinted polymers; MOFs: metal-organic
frameworks; OTA: ochratoxin A; OTB: ochratoxin B; PAT: patulin; STE: sterigmatocystin; TeA: tenuazonic acid; TEN: tentoxin; ZEN: zearalenone).

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Due to their multiple advantages, MIPs have been widely used for the four steps: (1) preparation of magnetic substrate, (2) functionalization of
extraction, preconcentration or clean-up of target analytes in food, the substrate, (3) MIPs synthesis, and (4) template removal. Nowadays,
biological or environmental samples, among others. However, some research on these materials is focused on the development of new syn­
drawbacks limit their use, including incomplete template removal, slow thesis strategies, such as sol-gel polymerization, electro-polymerization
mass transfer, poor accessibility, and low binding capacity [51]. In order or radical polymerization by atom transfer, as well as on the search for
to improve the isolation process, magnetic nanoparticles were intro­ effective compounds to achieve high yields and overcome possible
duced during the synthesis of MIPs due to their great properties, drawbacks [55]. Currently, MMIPs have attracted great attention for the
resulting in magnetic MIPs (MMIPs). The synthesis of MMIPs consists of extraction of mycotoxins in different complex matrices. Table 1

Table 1
Applications of magnetic molecularly imprinted polymers (MMIPs) for mycotoxin isolation (2016–2023).
Mycotoxin Sample Magnetic MIP core- Template Functional Cross- Analysis LOD (LOQ) Recovery Reusability Ref.
shell/type monomer linker rate (%) study
(cycles)
1
ZEN Cereal flours Fe3O4@SiO2 QUE 4-VP EGDMA UHPLC- 0.04 (0.1) ng g− 76–98 – [39]
MS/MS
ZEN Not applied Fe3O4@ QUE 4-VP EGDMA – – – 5 [40]
SiO2@polystyrene
− 1
ZEN Corn, rice, Fe3O4@SiO2–C=C Warfarin APTES TEOS HPLC-FLD 0.4 (0.9) ng kg 91–100 8 [61]
and wheat
1
ZEN Corn, rice, Fe3O4@SiO2–C=C–CD Warfarin APTES TEOS HPLC-FLD 0.1 (0.3) ng kg− 96–99 – [42]
and wheat
1
ZEN Refined corn Fe3O4@PDA QUE DA DA HPLC-FLD 0.7 ng mL− 94–101 7 [44]
oil
ZEN Waters Fe3O4@SiO2 CDHB CDHB – HPLC-FLD 2.3–2.4 (7.7–8.1) 100 10 [43]
ng g− 1
AF (B1, B2) Corn, Fe3O4@PDA DMC DA DA UHPLC-FLD 0.0004–0.002 ng 89–105 7 [23]
peanut, and mL− 1
edible oil
1
AF (B1, B2, Tea leaves Fe3O4@SiO2–C=C DMC MAA, 4-VP EGDMA UHPLC- 0.05–0.1 ng g− 76–95 6 [24]
G1, G2) and corn MS/MS
− 1
AFB1 Soy sauce Fe3O4@ DMC MAA EGDMA HPLC-FLD 0.4 ng mL 73–92 5 [31]
and vinegar SiO2@polystyrene– C=C
(MPCM–C=C)
1
OTA Corn, rice, Fe3O4@ Fmoc-d- APTES TEOS HPLC-FLD 0.7 ng mL− 84–116 5 [46]
and wheat SiO2@polystyrene Phe
(MPCM)
AF (B1, B2, Rice, wheat MGO/MOF–808@MIP DMC APTES TEOS FLD-GQDs 0.02–0.03 ng 96–102 8 [30]
G1, M1) flour, and and HPLC- mL− 1 and and
milk DAD 0.009–0.02 ng 95–105
mL− 1
AFB1 Animal liver Iron powder AFB1 HEMA EGDMA HPLC-FLD 0.05 ng mL− 1 78–83 10 [62]
STE Wheat Fe3O4 DT TAIC MBA HPLC-DAD 0.6 ng g− 1 88–97 6 [59]
STE Wheat, rice, Fe3O4@SiO2–MAPs DT AM EGDMA HPLC- 9 ng mL− 1 81–89 20 [60]
and millet UV–visible
1
PAT Apple, Fe3O4@SiO2–C=C 2- APTES TEOS HPLC-UV 3 (10) ng g− 86–96 8 [41]
grape, Oxindole
orange, and
pear juice
CIT Rice Fe3O4@OA 2-NA VPU, MAM EGDMA HPLC-DAD 0.7 (2) ng g− 1 94–98 30 [58]
DON, 3- Rice Fe3O4@OA DON MAA DVB UHPLC- 0.005–0.01 86–103 10 [49]
ADON, 15- MS/MS (0.02–0.03) ng
ADON, FUS- g− 1
X, T-2 toxin,
HT-2 toxin
AF (M1, B1, Infant MMISB DMC MAA EGDMA HPLC-MS/ 0.3–2 (1–6) ng 39–60 50 [32]
B2, G1, G2) formulas MS kg− 1
and cereal-
based baby
foods
1
PAT Apple MMISB 2- MAA EGDMA HPLC-MS/ 10 (50) ng g− 60–70 – [56]
Oxindole MS
PAT Apple juice Fe3O4@SiO2@CS-GO 2- AM APTMS HPLC-UV – 91–99 6 [57]
Oxindole

2-NA: 2-naphtholic acid; 3-ADON: 3-acetyldeoxynivalenol; 4-VP: 4-vinylpyridine; 15-ADON: 15-acetyldeoxynivalenol; AF: aflatoxin; AM: acrylamide; APTES: 3-ami­
nopropyltriethoxysilane; APTMS: 3-aminopropyl trimethoxysilane; CD: cyclodextrin; CDHB: cyclododecyl 2-hydroxy-4-(3-triethoxysilylpropylcarbamoyloxy)benzo­
ate; CIT: citrinin; CS-GO: chitosan-graphene oxide; DA: dopamine; DAD: diode array detector; DMC: 5,7-dimethoxycoumarin; DON: deoxynivalenol; DT: 1,8-
dihydroxyanthraquinone; DVB: divinylbenzene; EGDMA: ethylene glycol dimethacrylate; FLD: fluorescence detector; FL-GQDs: fluorescence emission of graphene
quantum dots; Fe3O4@SiO2–C=C: vinyl-modified magnetic nanoparticles covered by a silica layer; Fmoc-d-Phe: fluorenemethoxycarbonyl-D-phenylalanine; FUS-X:
fusarenon-X; HEMA: 2-hydroxyethyl methacrylate; HPLC: high performance liquid chromatography; LOD: limit of detection; LOQ: limit of quantification; MAA:
methacrylic acid; MAM: methacrylamide; MAPs: methacryloxypropyl triethoxysilane; MBA: N,N′-methylene bisacrylamide; MGO/MOF-808@MIP: Zr metal-organic
framework imprinted on the magnetic graphene oxide and coated with MIP; MMISB: magnetic molecularly imprinted stir-bar; MPCM: magnetic inverse photonic
crystal microsphere; MS/MS: tandem mass spectrometry; OA: oleic acid; OTA: ochratoxin A; PAT: patulin; PDA: dopamine; QUE: quercetin; STE: sterigmatocystin;
TAIC: Triallyl isocyanurate; TEOS: tetraethyl orthosilicate; UHPLC: ultra-high performance liquid chromatography; UV: ultraviolet; UV–visible: ultraviolet–visible;
VPU: N-3,5-bis(trifluoromethyl)phenyl-N′-4-vinylphenyl urea; ZEN: zearalenone.

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summarizes the research about MMIPs for the determination of myco­ developed for Alilou et al. proposing a combination of MOF and MIP for
toxins in the last years. AF extraction (AFM1, AFB1, AFB2 and AFG1) in wheat flour, rice and
The template molecule plays a key role in the design of high-affinity milk samples [30]. Specifically, a Zr-MOF was printed on the surface of
MIPs. Due to the toxicity of mycotoxins and their high cost, a dummy magnetic graphene oxide to form MGO/MOF-808, which was coated
template is often used. Ideally, this is a structurally related analogue, with a MIP layer. In addition, the use of MMIPs has been investigated in
which is stable and facilitates the preparation of MIPs [2]. Once tem­ animal liver for the selective recognition of AFB1 by Erdem et al. [62].
plates are removed from MIPs to create complementary cavities, they Consuming feed contaminated with mycotoxins can pose a risk to ani­
are typically not recovered from the elution solvent. Therefore, the use mal health, as mycotoxins can accumulate in the organism and can also
of environmentally friendly template molecules is important. Although be transferred to animal products such as milk or eggs [1].
it is not easy to avoid the use of organic compounds as template mole­ The determination of other mycotoxins as sterigmatocystin (STE) has
cules, dummy templates generally have lower toxicity than the target been carried out in wheat [59,60] and rice and millet [60] using MMIPs
molecules [54]. Based on the research, 2-oxindole is the dummy tem­ synthesized with a magnetite core and 1,8-dihydroxyanthraquinone
plate commonly employed to leave the binding site complementary in (DT) as a template. PAT was selectively extracted by a synthetized
form and function to PAT [41,56,57]. Fluorenemethox­ MMIP with a magnetic core based on Fe3O4@SiO2–C=C for its appli­
ycarbonyl-D-phenylalanine and 2-naphtholic acid were selected for OTA cation in different juices [41], and the isolation of citrinin (CIT) was
[46] and CIT [58], respectively. For the specific capture of STE, 1, carried out in rice samples using a semi-covalent MMIP with a magnetic
8-dihydroxyanthraquinone was used [59,60]. Pan et al. used the mole­ core modified with oleic acid [58]. In addition, due to the similar
cule of DON as a template for the recognition of six mycotoxins: T-2, structure of 3-ADON, 15-ADON, DON, T-2 toxin, FUS-X and HT-2 toxin,
HT-2, FUS-X, 3-acetyldeoxynivalenol (3-ADON), 15-acetyldeoxynivale­ their simultaneous recognition was proposed by Pan et al. using an oleic
nol (15-ADON), and DON [49]. In the case of AFs, 5,7-dimethoxycou­ acid-modified MMIP, using DON as mycotoxin template [49].
marin has been the most used molecule as dummy template [23,24, Although most publications on MMIPs for mycotoxin extraction in
30–32], and Erdem et al. used the target molecule (AFB1) as template complex matrices have been based on MSPE, the combination of MMIP
[33]. Different dummy templates were selected for the ZEN recognition and the stir bar sorptive extraction (SBSE) technique has also been
in MIPs: quercetin [39,40,44], warfarin [42,61] and cyclododecyl 2, investigated. Díaz-Bao et al. manufactured a MMIP as a stir-bar
4-dihydroxybenzoate [43]. (MMISB), combining magnetite synthesis and bulk polymerization, for
Moreover, magnetic substrate coating is a crucial step in the syn­ the determination of AFM1 in infant formulas (milk powder) and AFB1,
thesis of MMIPs. The coating with polymeric or silica matrices are AFG1, AFB2, AFG2 in baby food based on cereals [32]. Later, the same
intended to protect the core from dissolution or oxidation, activate or authors covered commercial glass-coated magnetic stir bars with poly­
functionalize the surface with functional groups and increase affinity, mer by a non-covalent bonding to obtain the MMISB and used it for the
hydrophobicity, or hydrophilicity. Magnetite (Fe3O4) is the most widely determination of PAT in apple [56].
used magnetic core for mycotoxin extraction [50,55]. In this sense, ZEN On the other hand, Sun et al. focused on the removal of PAT from
was determined in different food matrices by MMIPs with magnetite apple juice and for this purpose synthesized a MMIP with a magnetic
core coated with a silica layer (Fe3O4@SiO2) [39,40,42,43,61], and in core coated first with a silica layer, then with chitosan, and finally
one case using polydopamine as coating (Fe3O4@PDA) [44]. The MMIPs bonded to graphene oxide (Fe3O4@SiO2@CS-GO). The recovery values
developed by Cavaliere et al. allowed the detection and quantification of achieved were 98.8 % in the first extraction and 90.6 % after six ex­
ZEN in different cereals: tapioca and maize (7.5 ng g− 1), hulled wheat tractions [57], showing a high efficient removal of the mycotoxin.
(8.9 ng g− 1), whole wheat (9.7 ng g− 1), maize (8.5 ng g− 1) and rice The recognition properties of MMIPs are typically tested by
(15.0 ng g− 1) [39]. Piovesana et al. used oleic acid for the stabilization of comparing them with non-imprinted polymers (NIPs) prepared under
the nanoparticles (NPs) and added a polystyrene shell to develop the identical conditions but without a molecular template. Instead of a NIP,
MMIP [40]. Fu et al. used vinyl-modified Fe3O4@SiO2 NPs resulting in Calahorra-Rio et al. synthetized a control polymer (CIP), using a
Fe3O4@SiO2–C=C nanospheres with double bonds on the surface, and different template than that used for MMIP synthesis, to avoid the
the potential extraction for ZEN was investigated in wheat, corn and rice different morphology of shell NIPs due to the absence of template [43].
samples [61]. The same authors also investigated the binding of cyclo­ In the synthesis of MIPs, the functional monomers bind to the tem­
dextrin on the MIP surface. This combination provided two ZEN-specific plate to form the desired complexes, which are then immobilized by
recognition sites, corresponding to MIP and cyclodextrin, which were crosslinker polymerization. Functional monomers are typically organic
evenly distributed on the surface of the NPs, improving the ability to compounds, such as methacrylic acid (MAA) used in the determination
identify this mycotoxin in complex matrices [42]. Hu et al. synthetized a of AFs [24,31,32], PAT [56] and other mycotoxins [49], which could be
Fe3O4@PDA-based MMIP for the extraction of ZEN from refined corn oil toxic to marine and freshwater organisms [63]. As an alternative, ionic
[44] and Calahorra-Rio et al. developed a semi-covalent MMIP covered liquids are increasingly used as functional monomers in the synthesis of
with a silica layer in the presence of oleic acid which contributed to MIPs, because of their properties in line with green chemistry principles.
avoid Fe3O4 NPs aggregation during polymerization stage, and suc­ On the other hand, the most widely used crosslinking monomer in the
cessfully applied it to water samples [43]. synthesis of MIPs is ethylene glycol dimethacrylate (EGDMA). Sub­
Aflatoxin extraction has also been investigated using MMIPs in food stitutes for this compound are being investigated to achieve a more
samples as corn [23,24], peanut and edible oil [23], tea leaves [24], rice, environmentally friendly synthesis [54].
wheat flour and milk [30], and soy sauce and vinegar [31]. Suo et al. Most of the reported works have studied the reusability of the syn­
used a Fe3O4@PDA-based MMIP for the extraction of AFB1 and AFB2 thetized MMIPs (Table 1). For this purpose, a simple wash with organic
[23], and Tan et al. synthetized a MMIP with a Fe3O4@SiO2 magnetic solvents is performed, which is easy and cost-effective. In all of these
core vinyl functionalized for the recognition of AFG1, AFB1, AFG2, and studies, at least five adsorption-desorption cycles were achieved without
AFB2 [24]. Wang et al. synthetized magnetic inverse photonic crystal significant loss of yield or reproducibility of the material. Of note is the
microspheres (MPCM) vinyl-modified as a support material for MIPs to MMISB performed by Díaz-Bao et al., which remained intact after fifty
specifically recognize AFB1 from soy sauce and vinegar samples [31], extractions, demonstrating high resistance and stability [32]. This reuse
and hydroxyl-activated MPCMs for OTA determination in rice, corn and is consistent with green chemistry approaches by reducing the amount
wheat [46]. This three-dimensional ordered microporous material, of waste that can be released into the environment.
prepared by a microfluidic self-assembly approach, shows regular As regard detection techniques, the determination of mycotoxins
structures very interesting as supporting materials, improving both using MMIPs is widely performed by liquid chromatography coupled
binding capacity and mass transfer speed. A different approach was with fluorescence detection (FLD) [23,31,42–44,46,61,62] followed by

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A. Castell et al. Trends in Analytical Chemistry 178 (2024) 117826

tandem mass spectrometry (MS/MS) [24,32,39,49,56], diode array - Direct MOF magnetization. Magnetic NPs and MOF are separately
detection (DAD) [30,58,59] and UV–visible absorption spectrometry synthesized and subsequently mixed under sonication. The NPs
[41,57,60]. Alilou et al. used a fluorometer for a rapid analysis of AFs adhere to the MOF surface by electrostatic interactions.
due to their quenching effect on graphene quantum dots (GQDs) fluo­ - In situ growth of magnetic NPs. The prepared MOF is dispersed in the
rescence emission, and HPLC-DAD for discrimination of the extracted reagent mixture used to synthesize magnetic NPs, thus growing the
AFs [30]. NPs in the presence of the MOF. A requirement for the application of
this method is that the selected MOF must be stable under the syn­
2.3. Metal-organic frameworks (MOFs) thesis conditions of the NPs.
- Single-step MOF coating. The prepared magnetic NPs are added to a
MOFs are porous materials including in their composition organic solution containing the reagents for MOF formation. For satisfactory
ligands and metal ions bonded together to form an ordered three- growth of the MOF coating, surface modification of magnetic NPs
dimensional network. The crystal structure and its specific pore size with appropriate functional groups is desirable.
characteristics are determined by the selection of metal centers and - Layer-by-layer or step-by-step MOF growth. The method consists of
connection ligands, and therefore, their physicochemical properties can immobilizing the different MOF reagents on a functionalized sub­
be designed and adapted for a wide range of applications [64]. Their strate in a controlled sequence. First, the metal precursor is immo­
high porosity, versatile chemical composition, the possibility to adjust bilized on magnetic NPs, functionalized with chelating groups or
the pore surface area and the high thermal stability are the great ad­ with anion-exchange properties, followed by the organic ligand in a
vantages of MOFs [65]. second cycle. The thickness of the final MOF layer is determined by
In general, the synthesis of MOFs is not considered environmentally the number of cycles.
friendly due to the hazardous chemicals of non-renewable origin and the - MOF carbonization under inert atmosphere. MOF is used in this case
high temperatures required. However, the high surface area and high as a precursor material to generate a magnetic porous carbon (MPC)
tunability of these materials minimize the amount of sorbent required, used for extraction. The precursor MOF must contain metal ions to
reducing the environmental impact [66]. In addition, MOFs are form the magnetic NPs, and the organic linker acts as a carbon
commonly designed with non-toxic or minimally toxic metal ions such source. As a result, a porous carbon structure is produced in which
as Cu, Zr and Zn as metal ionic centers, and these materials are often the magnetic NPs are embedded. To prevent carbon oxidation,
reusable, which minimizes the generation of solid waste [67]. carbonization process is performed at high temperature under an
These materials, together with the use of magnetic sorbents such as inert atmosphere.
NPs, provide simple and rapid extractions, making them promising
materials for solid-phase extraction applications. MOFs are typically In the recent years, different magnetic MOFs have been used as
magnetized with magnetite and coated with polymers, silica, or carbon sorbents for the extraction of mycotoxins from food, including UiO-66,
nanostructures. Some approaches that have been described for magne­ MOF-5 and MIL-101. In addition, new combinations of MOFs have
tization of MOFs include [65]. been designed and their application for mycotoxin extraction have been
studied (Table 2). HPLC is the most used technique for the determination

Table 2
Applications of magnetic metal-organic frameworks (MOFs) for mycotoxin isolation (2016–2023).
Mycotoxin Sample Magnetic MOF type Organic Metal Analysis LOD (LOQ) Recovery Reusability Ref.
ligand ion rate (%) study (cycles)

AF (B1, B2, G1, Corn, rice and Fe3O4@SiO2@UiO-66- NH2BDC Zr4+ HPLC-FLD 0.2–0.9 87–101 7 [34]
G2) millet NH2@MON (0.5–3) ng
mL− 1
OTA wheat, corn, and Fe3O4@SiO2@UiO-66-NH2 NH2BDC Zr4+ OFHCL 0.3 ng mL− 1
82–111 4 [47]
bread immunosensor
AFB1 Not applied Fe3O4@UiO-66 H2BDC Zr4+ UHPLC-MS and – – 3 [36]
UHPLC-DAD
3+
AF (B1, B2, G1, Maize, wheat, MIL-101(Cr)@Fe3O4 H2BDC Cr UHPLC- MS/MS 0.02–0.06 84–108 – [25]
G2), OTA, watermelon, and (0.08–0.2) ng
OTB, T-2, HT- melon g− 1
2, DAS
AF (B1, G1), STE, Licorice MIL-101(Cr)@Fe3O4@PDA H2BDC Cr3+ UHPLC- MS/MS 0.01–0.09 79–116 5 [26]
OTA, ZEN (0.02–0.3) ng
g− 1
OTA Corn and peanuts Apt-MIL-101 (Cr)@Fe3O4 H2BDC Cr3+ UHPLC–MS/MS 0.07 (0.2) ng 83–108 12 [21]
L− 1
DON Wheat, corn, and MOF-5@Fe3O4 H2BDC Zn2+ OFHCL 47 ng L− 1 80–118 5 [68]
rice immunosensor
AF (B1, B2, G1, River water, well Fe3O4@SiO2@Cu/ NH2BDC Cu2+ HPLC-FLD 0.01–0.04 92–98 – [35]
G2) water and rice Ni–NH2BDC and (0.04–0.2) ng
Ni2+ mL− 1
AFB1, PAT, ZEN Not applied La–ZnFe2O4@Fe3O4@carbon H2BDC Zn2+ HPLC-DAD – – 5 [37]
and
La3+
DON, HT-2 Corn flour, Fe3O4@AMP&ZnCl2@McAbs AMP Zn2+ HPLC- MS/MS 2–5 (5–20) ng 87–101 3 [45]
toxin, T-2 wheat, and oat g− 1
toxin, ZEN flour

AF: aflatoxin; AMP: adenosine monophosphate; Apt-MIL-101: aptamer-modified MIL-101; DAD: diode array detector; DAS: diacetoxyscispernol; DON: deoxynivalenol;
Fe3O4@SiO2: magnetic nanoparticles covered by a silica layer; FLD: fluorescence detector; H2BDC: terephtalic acid; HPLC: high performance liquid chromatography;
LOD: limit of detection; LOQ: limit of quantification; McAbs: monoclonal antibodies; MIL-101(Cr)@Fe3O4@PDA: magnetic MIL-101 coated with dopamine; MON:
microporous organic network; MS/MS: tandem mass spectrometry; NH2BDC: 2-aminoterephthalic acid; OFHCL: optical fiber-based homogeneous chemiluminescent;
OTA: ochratoxin A; OTB: ochratoxin B; PAT: patulin; STE: sterigmatocystin; UHPLC: ultra-high performance liquid chromatography; UV: ultraviolet; ZEN: zearalenone.

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A. Castell et al. Trends in Analytical Chemistry 178 (2024) 117826

of mycotoxins in the samples investigated, coupled with FLD [34,35], 2.3.3. Other MOFs
DAD [36,37], MS [36] and MS/MS [21,25,26,45]. Wei et al. and Huang MOF-5 is based on the coordination of Zn(II) ions and H2BDC li­
et al. proposed an optical fiber-based homogeneous chemiluminescent gands. Huang et al. synthetized this type of MOF with Fe3O4 NPs for the
(OFHCL) immunosensor as an alternative to HPLC-MS [47,68]. selective extraction of DON in corn, wheat and rice based on MSPE, and
the detection was performed using an OFHCL immunosensor. As a
2.3.1. UiO-66 MOF result, DON was detected in 4 of the 12 blind wheat samples [68].
UiO-66 is the most investigated MOF of the UiO family, based on the Bimetallic MOFs have also been used for the extraction of myco­
coordination of Zr(IV) ions with terephthalic acid (H2BDC). Compared toxins from food samples. Rezaei et al. designed a MOF-on-MOF
to other MOFs composed of lower oxidation state metal ions, the higher combining Cu and Ni based on a layer-by-layer synthesis that overlays
oxidation state of Zr provides greater chemical and thermal stability one MOF on another. This bimetallic composite was applied for the
[65]. extraction of four AFs in water and rice samples by MSPE [35]. Of note is
This type of MOF has been applied for the determination of different the MPC material synthetized by Yang et al. based on the MOF
AFs and OTA in agricultural and food samples, as rice, millet, corn, carbonization procedure under inert atmosphere. A bimetallic MOF
wheat, and bread. Li et al. prepared a UiO-66 MOF using the step-by-step based on Zn and Fe was used as a precursor of a photocatalyst based on
method, by coating magnetite microspheres functionalized with amino ZnFe2O4 doped with La and combined with Fe3O4@carbon. The
groups with the MOF reagents, and then microporous organic network resulting composite degraded the 98.37% of AFB1, 97.35% of PAT and
(MON) was added onto the surface of Fe3O4@UiO-66-NH2 through a 98.52% of ZEN under UV irradiation [37].
coupling reaction, thus improving the adsorption efficiency of the sor­ On the other hand, Han et al. designed a MOF with a magnetite core
bent, as well as its stability and moisture resistance. Furthermore, the and monoclonal antibodies of DON, ZEN and HT-2/T-2 attached to the
reusability and stability of the proposed MOF was studied without sig­ surface for the specific binding of these mycotoxins. The aim was the
nificant loss of material performance after seven adsorption-desorption purification of oat, wheat, and corn flour from mycotoxins. The effi­
cycles. The presence of AFB1, AFG1, AFB2, and AFG2 was investigated ciency of this methodology was compared with an immunoaffinity col­
in rice, corn and millet samples, being AFB1 quantified in corn and umn and similar purification results of these mycotoxins were obtained
AFB1, AFB2 and AFG2 in millet [34]. with both treatments [45].
Wei et al. determined OTA in corn, wheat and bread samples using a
MOF based on amino functionalized Fe3O4 particles for the selective 2.4. Covalent organic frameworks (COFs)
recognition of the mycotoxin. OTA was quantified in 3 wheat, 3 maize
and 1 bread samples of the 20 blind samples analysed, at concentrations COFs are ordered crystalline porous materials composed of organic
ranging approximately from 4.5 to 13 ng g− 1 [47]. The approach applied monomers linked by covalent bonds, forming polymeric skeletons, and
by Song et al. was based on the AFB1 removal using a Fe3O4@UiO-66 non-covalent interactions for the formation of framework structures
MOF for its subsequent degradation by photocatalysis, thanks to the [29]. This porous structure has a high surface area and is composed of
porous structure of UiO-66 MOFs which enables AFB1 absorption and multi-aromatic rings with a variety of surface functional groups that
photocatalytic degradation, as well as the catalytic effect enhancement provide a high adsorption capacity for target compounds. In addition,
of Fe3O4. The adsorption and degradation efficiency of several combi­ COFs are very thermally and chemically stable [22]. Although the syn­
nations of MOFs and NPs of different sizes were evaluated, achieving thesis of COFs may be considered environmentally unfriendly due to the
specially high AFB1 elimination rates for MOFs with large-­ use of organic compounds, as is the case with MOFs, the exceptional
Fe3O4@small-UiO-66 and small-Fe3O4@large-UiO-66 [36]. properties of these materials minimize the environmental impact [66].
Due to the low weight of COFs and their poor dispersibility, the
2.3.2. MIL-101(Cr) MOF separation and recovery of analytes is costly. However, their magneti­
The MIL-101(Cr) is a MOF composed of Cr(III) ions and H2BDC as zation overcomes these drawbacks and makes them effective materials
organic ligand. The characteristics of this MOF are the high number of for the extraction of many contaminants [22]. Magnetic COFs have been
unsaturated Cr(III) sites for binding to electron-rich functional groups applied for the adsorption of mycotoxins in different foods in recent
and good water stability [25]. years (Table 3). For these applications, the synthesis consisted of a
Guo et al. used a MIL-101(Cr)@Fe3O4 synthetized by direct MOF COF-coated magnetite core formed by the combination of two functional
magnetization for the determination of several mycotoxins: OTA, OTB, monomers. The analyses of the enriched extracts were mainly performed
AFB1, AFB2, T-2, HT-2, AFG1, AFG2 and diacetoxyscirpenol (DAS), in by HPLC coupled to MS, except Yang et al. [48] who used an FLD de­
agricultural products as wheat, watermelon, maize and melon. The tector for the determination of OTA in vinegar, beer, and Chinese Baijiu.
proposed method was validated and applied to the analysis of 80 blind For the determination of AFM1 and AFM2 in milk, Li et al. used a
samples. Some mycotoxins were detected only in maize and wheat: COF composed of 2,5-dihydroxyterephthalaldehyde (DHTA) and 4′,5′-
AFB1 (< limit of quantification (LOQ)) and DAS (1.8–4.5 μg kg− 1) in bis(4-aminophenyl)-[1,1′:2′,1″-terphenyl]-4,4″-diamine (BAPTPDA) as
maize, and AFB1 (1.8–2.5 μg kg− 1), OTA (1.2–3.8 μg kg− 1), T-2 and HT- functional monomers, detecting AFM1 in 2 of 10 samples, at concen­
2 in wheat samples [25]. Tang et al. explored the extraction efficiency of trations of 0.0237 and 0.0243 μg kg− 1 [27]. In parallel, the same authors
a MIL-101(Cr) MOF and magnetite NPs functionalized with PDA for the investigated MSPE for extraction of AFs from rice, edible oil and milk
determination of five mycotoxins (AFB1, STE, AFG1, ZEN, OTA) in lic­ samples using a COF based on 1,2,4,5-tetrakis-(4-formylphenyl)benzene
orice samples. The rougher and more porous structure of Fe3O4@P­ (TFPB) and p-phenylenediamine (PPD). AFs were not found in milk
DA/MIL-101(Cr) compared to Fe3O4@PDA provided higher extraction samples, but AFB1and AFB2 were found in 19 oil samples and AFB2 in 8
efficiency for the five toxins. Additionally, the mesoporous structure of rice samples at a concentration range of 0.0409–0.158 μg kg− 1 [28]. Wei
the MOF seemed to reduce sample matrix effects. Only OTA was et al. used 1,3,5-triformylphloroglucinol (Tp) and benzidine as func­
detected in the samples, below the LOQ in all cases and the European tional monomers for the synthesis of the COF. Ten mycotoxins including
Union maximum residue limit [26]. The specific binding of OTA in a ENNs, AFs and OTs were investigated in maize, with AFB1 detected in
magnetic MIL-101(Cr) MOF was studied by Zhang et al. when immo­ two of ten blind samples at 0.81 and 1.01 μg kg− 1 [29]. COF synthesis by
bilizing OTA aptamers on its surface, which increased the selectivity template polymerization method was employed by Wang et al. using the
with respect to the MOF without aptamer modification. The extraction monomers 1,3,5-tris-(4-aminophenyl)triazine (TAPT) and DHTA for the
capacity of this material remained stable after 12 uses and the procedure determination of several mycotoxins in five fruits: tenuazonic acid
was applied to corn and peanut samples [21]. (TeA), alternariol (AOH), tentoxin (TEN), alternariol methyl ether
(AME), altenuene (ALT), ALS, AFB1, OTA and ZEN. ALT was detected in

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A. Castell et al. Trends in Analytical Chemistry 178 (2024) 117826

Table 3
Applications of magnetic covalent organic frameworks (COFs) for mycotoxin isolation (2016–2023).
Mycotoxin Sample Magnetic COF type Functional Analysis LOD (LOQ) Recovery Reusability Ref.
monomers rate (%) study (cycles)

AF (M1, M2) Milk Fe3O4@COF DHTA and HPLC- 0.07–0.08 85–107 8 [27]
(BAPTPDA–DHTA) BAPTPDA MS/MS (0.02–0.03) ng
g− 1
AF (B1, B2, G1, G2) Milk, edible oil, and rice Fe3O4@COF TFPB and PPD HPLC- 0.01–0.05 76–113 8 [28]
1
(TFPB–PPD) MS/MS (0.05–0.2) ng g−
AF (B1, B2, G1, G2), Maize Fe3O4@COF(Tp–BD) Tp and BD HPLC- 0.02–2 (0.07–6) 74–105 5 [29]
OTA, OTB, ENN (A, MS/MS ng g− 1
B, A1, B1)
TeA, AOH, TEN, AME, watermelon, hawthorn, Fe3O4@COF TAPT and UHPLC- 0.01–0.5 (0.05–1) 74–112 – [38]
ALT, ALS, AFB1, melon, tomato, and (TAPT–DHTA) DHTA MS/MS ng g− 1
OTA, ZEN strawberry
1
OTA Beer, vinegar, and Fe3O4@COF TAPB and HPLC-FLD 0.03 ng mL− 72–111 6 [48]
Chinese Baijiu (DHTA–TAPB) DHTA
ZEN, α-ZEL, β-ZEL, Maize, egg, and milk Fe3O4@COF Tp and TAPB UHPLC- 0.003–0.02 81–90 10 [22]
α-ZAL, β-ZAL (TAPB–Tp) MS/MS (0.01–0.05) ng
g− 1

α-ZAL: α-zearalanol; α-ZEL: α-zearalenol; β-ZAL: β-zearalanol; β-ZEL: β-zearalenol; AF: aflatoxin; ALS: altenusin; ALT: altenuene; AME: alternariol methyl ether; AOH:
alternariol; BAPTPDA: 4′,5′-bis(4-aminophenyl)-[1,1′:2′,1″-terphenyl]-4,4″-diamine; BD: benzidine; DHTA: 2,5-dihydroxyterephthalaldehyde; ENN: enniatin; FLD:
fluorescence detector; HPLC: high performance liquid chromatography; LOD: limit of detection; LOQ: limit of quantification; MS/MS: tandem mass spectrometry; OTA:
ochratoxin A; OTB: ochratoxin B; PPD: p-phenylenediamine; TAPB: 1,3,5-tris(4-aminophenyl)benzene; TAPT: 1,3,5-tris-(4-aminophenyl)triazine; TeA: tenuazonic
acid; TEN: tentoxin; TFPB: 1,2,4,5-tetrakis-(4-formylphenyl)benzene; Tp: 1,3,5-triformylphloroglucinol; UHPLC: ultra-high performance liquid chromatography; ZEN:
zearalenone.

all fruits (hawthorn, watermelon, melon, strawberry and tomato), TeA extraction efficiency, and material reusability. In addition to these
in strawberry and tomato, AOH in strawberry, hawthorn and tomato, criteria, MSPE techniques and the synthesis of nanomaterials should
AME in melon and hawthorn, TEN in tomato and hawthorn, and ALS in comply with ecological criteria. Although the use of these materials
tomato, strawberry, melon and hawthorn [38]. The determination of often leads to lower power requirements and less sample and solvent
OTA in vinegar, beer, and Chinese Baijiu carried out by Yang et al. was consumption, the environmental sustainability of these methods de­
performed using a COF composed of 1,3,5-tris(4-aminophenyl)benzene pends on the sorbent, coating, and application. The integration and
(TAPB) and DHTA [48]. Wang et al. determined ZEN and its metabolites unification of the evaluation of these materials would facilitate their
in eggs, milk and maize samples using a COF formed by Tp and TAPB practical and routine application in food safety control.
synthetized by template-mediated precipitation polymerization, result­ MIPs, MOFs and COFs magnetic materials offer many advantages for
ing in a stable and reusable material up to 10 times. ZEN, α-zearalenol research into the monitoring of mycotoxins in food. However, some of
(α-ZEL) and β-zearalenol (β-ZEL) were detected in maize [22]. the challenges faced are improved material properties, environmentally
friendly synthesis, or automation of sample preparation, which can
3. Conclusions improve the strategy by minimizing errors and streamlining the detec­
tion process. Expanded research is expected to improve the detection
Magnetic materials have been shown to provide numerous advan­ and monitoring of mycotoxins in food by exploiting the multiple ad­
tages for the extraction of mycotoxins in complex matrices. These ma­ vantages of magnetic nanomaterials.
terials have good dispersibility in solvents, high surface area and the
possibility of modifying and functionalizing their surface, improving the CRediT authorship contribution statement
performance and simplifying the sample treatment by allowing easy
separation with a magnet. Thus, interest in the synthesis and application Ana Castell: Writing – original draft, Visualization, Resources,
of these materials for mycotoxin isolation, both for quantitation and Investigation, Data curation. Natalia Arroyo-Manzanares: Writing –
removal purposes, has increased in recent years. MIPs bind to the ana­ review & editing, Visualization, Supervision. Pilar Viñas: Writing –
lyte of interest via specific sites in terms of functionality, size, and shape, review & editing, Project administration, Funding acquisition. Ignacio
resulting in high affinities. AFs and ZEN are the most studied mycotoxins López-García: Writing – review & editing, Visualization, Funding
in foods for their extraction by magnetic MIPs. High porosity, versatile acquisition, Data curation. Natalia Campillo: Writing – review &
chemical composition, and the possibility of adjusting the pore surface editing, Supervision, Resources, Conceptualization.
are the great advantages of MOFs, which together with the use of
magnetic NPs provide easy and fast extractions. UiO-66 and MIL-101 Declaration of competing interest
(Cr) are the most used MOFs for mycotoxins, although new combina­
tions of MOFs have been designed and their application has been stud­ The authors declare that they have no known competing financial
ied. The magnetization of COFs makes them effective materials for interests or personal relationships that could have appeared to influence
isolation of mycotoxins, since they are composed of multi-aromatic rings the work reported in this paper.
with a variety of surface functional groups that enable a high adsorption
capacity. These materials have been applied for the extraction of my­ Data availability
cotoxins such as ENNs, ALS or Alternaria mycotoxins that had not been
previously studied by MIPs or MOFs. HPLC coupled to MS/MS or FLD are Data will be made available on request.
the most commonly used techniques for accurate detection of myco­
toxins. Other detectors such as DAD and UV–vis have also been widely
Acknowledgements
combined with HPLC.
Some of the specific parameters often evaluated for material char­
This research was funded by the Spanish MCIN (Project PID2021-
acterization are adsorption capacity, selectivity, chemical stability,
123201NB-I00). A. Castell acknowledges a fellowship from University of

8
A. Castell et al. Trends in Analytical Chemistry 178 (2024) 117826

Murcia (AEIP2020-0005). [21] Q. Zhang, Y. Yang, Y. Zhi, X. Wang, Y. Wu, Y. Zheng, Aptamer-modified magnetic
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