With the continuous development of nanotechnology and materials science, a variety of nanoscale materials have been developed for purifying complex food matrices or providing response signals for accurate and rapid detection of various mycotoxins in foods. Mycotoxins are highly toxic, widely contaminated, and difficult to remove . They can enter and enrich the food chain through foodstuffs and animal-derived products such as meat, milk, and eggs and ultimately penetrate into organisms, causing reproductive abnormalities, immunosuppression, cancer, and other serious diseases, which pose a serious threat to human health.
The United States | Total amount of AFB in food: <20 μg/kg; DON: <1000pg/kg, ZEN: <100 pg/kg; Milk and dairy products: AFM1 ≤ 0.5 μg/kg. |
European Union | Agricultural products: Total amount of AFs: <4 μg/kg, AFB1: <2 μg/kg, OTA: <3 μg/kg, DON: <1000 μg/kg, ZEN: <50 μg/kg; Infant foods: Total amount of AFB: <2 μg/kg, AFB1 <0.1 μg/kg, AFM1: <0.025 μg/kg, OTA: <0.5 μg/kg, DON: <150 μg/kg, ZEN: <20 μg/kg |
China | Corn, peanuts, and their products: AFB1: < 20 μg/kg, OTA: <5 μg/kg, DON: <1000 μg/kg, ZEN < 60 μg/kg; Other grains, beans, and fermented foods: AFB1: <5 μg/kg; Infant foods: AFB1: 5 μg/kg, AFM1: < 0.5μg/kg; Fresh milk and dairy products: AFM1: < 0.5μg/kg; Rice and vegetable oils (except corn oil and peanut oil): AFB1: <10 μg/kg. |
Japan | Peanuts and their products: AFB1: <10 μg/kg; Wheat: DON: <1100 μg/kg; Apple juice: Patulin: <50 μg/kg. |
Currently, instrumental analysis techniques based on chromatographic separation, mass spectrometry, or spectroscopy remain the primary strategies for accurately detecting mycotoxins in food, widely accepted as standardized methods by international organizations [24–26][17][18][19]. Large-scale analytical instruments, typically equipped with sensitive detectors and data analysis modules, can successfully detect trace levels of toxin targets with advantages of accuracy, reproducibility, and reliability [27,28][20][21]. However, various mycotoxins may coexist at extremely low concentrations in food, and considering the complexity of food matrices, it is necessary to purify the food matrix during the detection process while achieving the enrichment of low-concentration mycotoxins to meet the requirements of instrument analysis [29][22]. In response to this challenge, novel purification materials with nanoscale features or exceptional structural characteristics have been continuously developed and used in combination with various large-scale analytical instruments, such as chromatography and mass spectrometry, achieving accurate and sensitive detection of mycotoxins in complex food matrices [30–32][23][24][25]. TableTable 2 2 illustrates the application of various nanoscale materials in solid-phase extraction (SPE) and solid-phase microextraction (SPME) processes for the detection of mycotoxins in food.
Materials/Methods | Mycotoxins | Substrates | Properties of Materials | Results | Ref. | |
---|---|---|---|---|---|---|
SPE | ||||||
PDA-IL-NFsM SPE coupled with UPLC-MS/MS |
AFB1, AFB2, AFG1, AFG2, ST, FB1, FB2, OTA, ZEN, HT-2, T-2, DON, 3-AcDON, NIV, 15-AcDON | Corn, wheat | Various interception mechanisms with the target through hydrogen bonding, π-π interaction and electrostatic or hydrophobic interaction; good simultaneous adsorption performance; significantly reducing the matrix effect | Various interception mechanisms with the target through hydrogen bonding, π-π interaction, and electrostatic or hydrophobic interaction; good simultaneous adsorption performance; significantly reducing the matrix effect | Linear range:: 1.0–2000 μg/kg; LOD:: 0.04–4.21 μg/kg; LOQ:: 0.13–14.03 μg/kg; Recovery:: 80.79–112.37 % ((RSD:: 2.91–14.82 %,, n = 4)) |
[33][26] |
Fe3O4@COF Magnetic SPE coupled with UHPLC-MS/MS Magnetic SPE coupled with UHPLC-MS/MS |
AFB1, OTA, ZEN, TEN, ALT, ALS, AME, AOH, TEA | Fruits | Abundant aromatic rings and carbonyl groups in Fe3O4@COF structure; through the strong π-π interaction and hydrogen bond between mycotoxin and Fe to realize effective enrichment of target mycotoxin | Linear range:: 0.05–200 μg/kg; LOD:: 0.01–0.50 μg/kg; LOQ:: 0.10–1.00 μg/kg; Recovery:: 74.25–111.75 % ((RSD:: 2.08–9.01 %,, n = 5)) |
[34][27] | |
PDA@Fe3O4-MWCNTs Magnetic SPE coupled with HPLC-FLD |
AFB1,, AFB2,, AFG1,, AFG2、, OTA、, OTB | Edible vegetable oils | Good water solubility and dispersibility; largely eliminating the influence of matrix effect | Linear range:: 1–100 μg/kgL; LOD:: 0.2–0.5 μg/kg; LOQ:: 0.6–1.5 μg/kg; Recovery:: 70.15–89.25 % ((RSD:: ≤ 6.4 %,, n = 6)) |
[35][28] | |
rGO/AuNPs SPE coupled with UHPLC-MS/MS |
AFB1, AFM1, OTA, ZEA, α-ZOL, β-ZOL, ZAN, α-ZAL, β-ZAL | Milk | Good adsorbability; adding AuNPs increases the distance between graphene layers and minimizes agglomeration | Linear range:: 0.02–200 ng/mL; LOD:: 0.01–0.07 ng/mL; LOQ:: 0.02–0.18 ng/mL; Recovery:: 70.1–111.1 % ((RSD:: 2.0–11.1 %,, n = 5)) |
[36][29] | |
MIL-101(Cr)@Fe3O4 Magnetic SPE coupled with UHPLC-MS/MS |
AFB1, AFB2, AFG1, AFG2, OTA, OTB, T-2, HT-2, DAS | Maize, wheat, watermelon, and melon | Magnetic separation and adsorption capabilities involving polar or nonpolar forces, hydrogen bonding forces, and π-π conjugation with mycotoxin-rich functional groups | Linear range: 0.2–100 ng/mL LOD: 0.02–0.06 μg/kg; LOQ: 0.08–0.2 μg/kg Recovery: 83.5–108.5 % (RSD: 1.6–10.4 %, n = 5) |
[37][30] | |
Fe3O4@SiO2-NH2 Magnetic SPE coupled with ELISA |
AFB1 | Pixian douban | Rapid separation and enrichment under the external magnetic field; strong chemical stability, storage stability, and specificity combined with aptamer | Linear range: 0.5–2.0 ng/mL; LOD: 0.17 ng/mL; LOQ: 0.48 ng/mL; Recovery: 80.19–113.92 % (RSD: 2.30–7.28 %, n = 3) |
[38][31] | |
HAS SPE coupled with HPLC-PHRED-FLD |
AFB1 | Vegetable oils | Outstanding adsorption properties due to the large number of functional group hydrogen bonding, hydrophobicity, and π-π interactions; minimizing the pretreatment time and the amounts of organic solvents | Linear range: 0.10–50 μg/kg; LOD: 0.03–0.09 μg/kg; LOQ: 0.1–0.3 μg/kg; Recovery: 66.9–118.4 % (RSD: ≤ 7.2 %, n = 6) |
[39][32] | |
UIO-66-NH2@MIPs SPE coupled with HPLC |
AFB1, AFB2, AFG1, AFG2 | Wheat, rice, corn, soybean | Uniform and stable; the unique pore structure effectively improving the selective adsorption capacity; excellent affinity and selectivity | Linear range: 0.20–45 μg/kg; LOD: 0.06–0.13 μg/kg; LOQ: 0.24–0.45 μg/kg; Recovery: 74.3–98.6 % (RSD: 1.0–5.9 %, n = 6) |
[40][33] | |
MWCNT-COOH + C18 SPE coupled with UPLC-MS/ MS |
21 mycotoxins (AFs, OTA, OTB, ZEN, T-2, ZEN et al.) | Corn, wheat | Significantly reducing the matrix effect; high-throughput screening of various targets; greatly improving the detection efficiency | LOQ: 0.5–25 μg/L; Recovery: 75.6–110.3 % (RSD: 0.3–10.7 %, n = 5) |
[41][34] | |
HNTs-HMIPs SPE coupled with HPLC-FD (Figure 1a) |
ZEN | Rice corn, red beans, oats, wheat | Hollow imprinted polymer; excellent adsorption due to the loose and porous characteristics | LOD: 0.5 μg/kg; LOQ: 4.17 μg/kg (Oat), 1.8 μg/kg (Wheat); Recovery: 77.13–102.4 % (RSD: ≤ 5.59 %, n = 6) |
[42][35] | |
SPME | ||||||
AuNPs SPME coupled with UHPLC-MS/MS |
PAT | Apple juice, fresh apple, apple baby food, orange juice | Capillary monolithic column directly modified by AuNPs; high specificity and high affinity | Linear range: 8.11–8.11 × 103 pmol/L; LOD: 2.17 pmol/L; Recovery: 85.4–106 % (RSD: 4.1–7.3 %, n = 5) |
[43][36] | |
MAA-co-DVB SPME coupled with HPLC |
AFB1, ZEN, STEH | Rice | High-strength micro/nanostructure containing a large number of acrylic groups forming hydrogen bonds with groups in the target structure; effectively overcoming the matrix effect | Linear range: 0.01–1.0 mg/kg; LOD: 0.689–2.030 μg/kg; LOQ: 5.36–14.4 μg/kg Recovery: 86.0–102.8 % (RSD: ≤ 4.8 %, n = 4) |
[44][37] | |
Fe3O4@SiO2@Cu/Ni-NH2BDC Dispersive SPME coupled with HPLC-FLD |
AFB1, AFB2, AFG1, AFG2 | River water, well water, rice | Chemical bonds formed between three components making the adsorbent more stable and magnetic; rapid separation | Linear range: 0.11–79.2 ng/mL; LOD: 0.01–0.04 ng/mL; LOQ: 0.04–0.15 ng/mL; Recovery: 92.0–97.8 % (RSD: 4.1–7.6 %) |
[45][38] | |
MOF+VB3 Dispersive SPME coupled with HPLC-FLD |
PAT, OTA, AFB1, AFB2, AFG1, AFG2 | Fruit juices, milk |
Green organic linker; high surface area, high adsorption capacity, and excellent porosity to form a new green adsorbent | Linear range: 42.8–1 × 106 ng/L; LOD: 11.3–48.2 ng/L; LOQ: 42.8–161.6 ng/L; Recovery: 64.0–87.0 % (RSD: ≤5 %, n = 3) |
[46,47][39][40] |