随着纳米技术和材料科学的不断发展,已经开发出各种纳米级材料,用于复杂食品基质的纯化或提供响应信号,以实现食品中各种霉菌毒素的准确快速检测。霉菌毒素具有剧毒、广泛污染且难以清除。它们可以通过食品和肉、奶、蛋等动物源性产品进入和丰富食物链,最终渗透到生物体内,引起生殖异常、免疫抑制、癌症等严重疾病,对人体健康构成严重威胁。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.
美国The United States | 食物中Total amount of AFB的总量:<20微克/千克;唐:<1000皮克/公斤,禅宗:<100皮克/公斤 in food: <20 μg/kg; DON: <1000pg/kg, ZEN: <100 pg/kg; 牛奶和乳制品:原子力显微镜Milk and dairy products: AFM1 ≤0.5微克/千克。 0.5 μg/kg. |
欧盟European Union | 农产品:Agricultural products: Total amount of AF总量:<4微克/千克,s: <4 μg/kg, AFB1:: <2 微克/公斤, OTA: <3 微克/公斤, 唐:μg/kg, OTA: <3 μg/kg, DON: <1000 微克/公斤, 禅宗: <50 微克/公斤μg/kg, ZEN: <50 μg/kg; 婴儿食品:Infant foods: Total amount of AFB总量:<2微克/千克,: <2 μg/kg, AFB1 <0.1微克/千克,原子力显微镜 μg/kg, AFM1:: <0.025 微克/千克, OTA:μg/kg, OTA: <0.5 微克/千克, 唐:μg/kg, DON: <150 微克/千克, 禅宗: <20 微克/千克μg/kg, ZEN: <20 μg/kg |
中国China | 玉米、花生及其制品:空军基地Corn, peanuts, and their products: AFB1:: <20微克/千克,OTA:<5微克/千克,唐:<1000微克/千克,禅<60微克/千克 20 μg/kg, OTA: <5 μg/kg, DON: <1000 μg/kg, ZEN < 60 μg/kg; 其他谷物、豆类和发酵食品:空军基地Other grains, beans, and fermented foods: AFB1:: <5微克/千克 μg/kg; 婴儿食品:空军基地Infant foods: AFB1:: 5 微克/千克, 原子力显微镜μg/kg, AFM1:: < 0.5微克/千克μg/kg; 鲜奶和乳制品:原子力显微镜Fresh milk and dairy products: AFM1:: < 0.5微克/千克μg/kg; 大米和植物油(玉米油和花生油除外):空军基地 |
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]. 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]. 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]. 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]. Table 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.
材料/方法Materials/Methods | 霉菌毒素Mycotoxins | 基质Substrates | 材料的性质Properties of Materials | 结果Results | 裁判。Ref. |
---|---|---|---|---|---|
Rice and vegetable oils (except corn oil and peanut oil): AFB | |||||
1 | |||||
: | : <10微克/千克 μg/kg. | ||||
日本Japan | 花生及其制品:空军基地Peanuts and their products: AFB1:: <10微克/千克 μg/kg; 小麦:唐:Wheat: DON: <1100微克/千克 μg/kg; 苹果汁:棒曲霉素:Apple juice: Patulin: <50微克/公斤。 μg/kg. |
SPE | ||||||
PDA-IL-NFsM SPE与 coupled with UPLC-MS/MS耦合 |
空军基地AFB1,, 空军基地AFB2,, AFG1,, AFG2,, ST,, FB1,, FB2,, 太田, 禅宗, HT-2, T-2, 唐, 3-阿克顿, NIV, 15-阿克唐OTA, ZEN, HT-2, T-2, DON, 3-AcDON, NIV, 15-AcDON | 玉米、小麦Corn, wheat | 通过氢键、π π相互作用、静电或疏水相互作用与靶材的各种截获机理;良好的同时吸附性能;显著降低基质效应 | 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 | 线性范围Linear range:1.0–2000 μg/kg; LOD: 0.04–4.21 微克μg/千克kg; LOQ: 0.13–14.03 微克μg/千克kg; 回收率Recovery: 80.79–112.37 % (RSD: 2.91–14.82 %, n = 4) |
[33] |
铁Fe3O4 @COF 磁性 SPE 与 UHPLC-MS/MS 耦合@COF Magnetic SPE coupled with UHPLC-MS/MS |
空军基地AFB1,, 太田, 禅宗, 十, 阿尔特, 阿尔特, 阿美, 奥赫, 茶OTA, ZEN, TEN, ALT, ALS, AME, AOH, TEA | 水果Fruits | Abundant aromatic rings and carbonyl groups in Fe中丰富的芳环和羰基3O4@COF结构 structure;通过霉菌毒素与铁之间强π π相互作用和氢键,实现目标霉菌毒素的有效富集 through the strong π-π interaction and hydrogen bond between mycotoxin and Fe to realize effective enrichment of target mycotoxin | 线性范围Linear range:0.05–200 μg/kg; LOD: 0.01–0.50 微克μg/千克kg; LOQ: 0.10–1.00 微克μg/千克kg; 回收率Recovery: 74.25–111.75 % (RSD: 2.08–9.01 %, n = 5) |
[34] | |
PDA@Fe3O4-MWCNTs 磁性Magnetic SPE与 coupled with HPLC-FLD耦合 |
空军基地AFB1, 空军基地AFB2, AFG1, AFG2、OTA、OTB | 食用植物油Edible vegetable oils | 良好的水溶性和分散性Good water solubility and dispersibility;在很大程度上消除了基质效应的影响 largely eliminating the influence of matrix effect | 线性范围Linear range:1–100 微克/升μg/kg; LOD: 0.2–0.5 微克μg/千克kg; LOQ: 0.6–1.5 微克μg/千克kg; 回收率Recovery: 70.15–89.25 % (RSD: ≤ 6.4 %, n = 6) |
[35] | |
rGO/AuNPs SPE 与coupled with UHPLC-MS/MS 耦合 |
AFB1, AFM1, OTA, ZEA, α-ZOL, β-ZOL, ZAN, α-ZAL, β-ZAL | 牛奶Milk | 吸附性好Good adsorbability;添加AuNP可增加石墨烯层之间的距离并最大限度地减少团聚 adding AuNPs increases the distance between graphene layers and minimizes agglomeration | 线性范围Linear range:0.02–200 纳克/毫升ng/mL; 最低载荷LOD:0.01–0.07 纳克/毫升ng/mL; LOQ: 0.02–0.18 纳克ng/毫升mL; 回收率Recovery: 70.1–111.1 % (RSD: 2.0–11.1 %, n = 5) |
[36] | |
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] | |
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] | |
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] | |
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] | |
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] | |
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] | |
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] | |
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] | |
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] | |
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] |