基于碳基磁性材料的磁固相萃取技术在食品分析应用中的研究进展

Research progress in the application of magnetic solid phase extraction based on carbon based magnetic materials in food analysis

食品中残留的痕量有毒物质严重威胁人体健康,对其进行分析十分必要。然而,食品中有毒物质种类多、量少、基质复杂,需选择适当的样品预处理技术进行提取和净化。磁固相萃取(MSPE)因具有操作简单、省时快速、无需离心过滤、环境友好等优点,被认为是一种高效的样品预处理技术并应用于食品分析中。MSPE中使用的磁性吸附剂的吸附容量和选择性是影响MSPE萃取效率和选择性高低的关键,对所建立分析方法的准确度起着关键作用。碳基磁性材料是具有价格低廉、来源丰富、比表面积大、化学稳定性好、吸附容量高、绿色环保等优点的一类新型功能性磁性材料,可以富集不同性质的有机、无机分析物,在环境分析、生物检测、污染治理等多个领域取得了较大进展。近年来,基于碳基磁性材料的MSPE技术在食品分析预处理领域逐渐得到应用,但尚处于起步阶段,存在巨大的应用潜力。该文以碳基类别(碳纳米管、石墨烯、金属有机骨架衍生碳、活性炭等)为主线,综述了采用MSPE技术,以碳基磁性材料为吸附剂,对食品样品中酯类、真菌毒素、多环芳烃、抗生素、生物碱、酚类、维生素、抗菌药等物质进行萃取,进而采用液相色谱法等进行分析的应用实例,同时阐述了该技术存在的问题,并对其发展方向做出了展望。该综述将为基于碳基磁性材料的MSPE技术在食品分析中的广泛应用提供理论依据和技术支撑。

Trace toxic substances in food pose a serious threat to human health,and need to be detected and analyzed to ensure food safety.However,there are many kinds of toxic substances in food,with small amounts and complex matrices,making it necessary to select an appropriate sample pretreatment technology for extraction and purification.There are some disadvantages to sample pretreatment methods such as solid phase extraction and liquid-liquid extraction,in terms of poor selectivity,significant influence of matrix interference,large sample requirement,long extraction time,use of a large amount of harmful organic solvents,and cumbersome and time-consuming operation.Magnetic solid phase extraction(MSPE)combines the advantages of magnetic separation and traditional SPE technology,avoids time-consuming column loading,and can extract the target analyte efficiently.Because of its advantages,in that it has simple operation,is time-saving and fast,requires no centrifugal filtration,and is environmentally friendly,it is considered an efficient sample pretreatment technology and applied in food analysis.The adsorption capacity and selectivity of the magnetic adsorbent used in MSPE are the key factors affecting the extraction efficiency and selectivity of MSPE,and play a key role in the accuracy of the established method.Carbon-based magnetic materials are a type of new functional magnetic materials prepared by the co-precipitation of carbon-based materials(carbon nanotubes,graphene,metal-organic framework-derived carbon,or activated carbon)and magnetic materials.In order to endow carbon-based magnetic materials with the advantages of both,carbon materials and magnetic materials,while also reflecting the advantages of high specific surface area,good stability,low cost,environmental friendliness,excellent physical and chemical properties,high porosity,and high adsorption capacity,proper functional modification is needed.Carbon-based magnetic materials modified by functionalization can efficiently enrich organic and inorganic analytes with different properties,and have seen significant progress in environmental analysis,biological detection,pollution control,and other fields.In recent years,MSPE technology based on carbon-based magnetic materials has been gradually applied in food analysis and pretreatment,but its use is still in infancy and holds immense application potential.Reference to more than 50 papers published in SCI and Chinese core journals over the past four years reveals that carbon-based materials include carbon nanotubes modified by functional groups,reagents,or materials;graphene,graphene oxide,and reduced graphene oxide;carbon derived from a gold organic framework;activated carbon biochar;and nanodiamond.The harmful substances in food samples include esters,mycotoxins,polycyclic aromatic hydrocarbons,antibiotics,alkaloids,phenols,vitamins,and antibiotics.Based on the classification of carbon-based materials,this review reveals that carbon-based magnetic materials have good preconcentration ability for harmful substances in food samples.MSPE can be combined with GC-MS,liquid chromatography-high resolution mass spectrometry(LC-HRMS),ultra-fast liquid chromatography-tandem mass spectrometry(UFLC-MS/MS),ultra high performance liquid chromatography-Q-Exactive high resolution mass spectrometry(UHPLC-Q-Exactive HRMS),high performance liquid chromatography-diode array detection(HPLC-DAD),gas chromatography micro-electron capture detection(GC-μECD),high performance liquid chromatography fluorescence with post-column photochemical derivatization(HPLC-PCD-FLD),and HPLC-UV to analyze food samples.These combined technologies have high accuracy and recovery.However,the synthesis methods of carbon-based magnetic materials such as carbon nanotubes and graphene,incur high energy consumption and high cost,and involve complex processes,which limit their application.Therefore,a carbon-based magnetic adsorbent with low cost,high selectivity,and high extraction efficiency was developed by further exploring functional modification with biochar as a carbon base.This is a very promising direction to develop MSPE technology utilizing biochar-based magnetic materials for food sample pretreatment.This review provides a theoretical basis and technical support for the wide application of carbon-based magnetic materials in MSPE technology for food analysis.