Article(id=1322594732895748653, tenantId=1146029695717560320, journalId=1283840372199657495, issueId=1322594687962169764, articleNumber=null, orderNo=null, doi=10.3724/SP.J.1123.2025.12010, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1765468800000, receivedDateStr=2025-12-12, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793260756943, onlineDateStr=2026-10-29, pubDate=1791388800000, pubDateStr=2026-10-08, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793260756943, onlineIssueDateStr=2026-10-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793260756943, creator=13701087609, updateTime=1793260756943, updator=13701087609, issue=Issue{id=1322594687962169764, tenantId=1146029695717560320, journalId=1283840372199657495, year='2026', volume='44', issue='10', pageStart='1103', pageEnd='1261', issueExtLink='null', onlineDate='null', pubDate='1791388800000', pubDateStr='2026-10-08', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1793260746231, creator='13701087609', updateTime=1793261985251, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322599884910350425, tenantId=1146029695717560320, journalId=1283840372199657495, issueId=1322594687962169764, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322599884910350426, tenantId=1146029695717560320, journalId=1283840372199657495, issueId=1322594687962169764, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1175, endPage=1189, ext={EN=ArticleExt(id=1322594733667500590, articleId=1322594732895748653, tenantId=1146029695717560320, journalId=1283840372199657495, language=EN, title=Research progress of magnetic microporous organic networks in magnetic solid-phase extraction, columnId=1284557502389928401, journalTitle=Chinese Journal of Chromatography, columnName=Reviews, runingTitle=null, highlight=null, articleAbstract=

Recently, magnetic microporous organic networks (MMONs) have emerged as a novel class of adsorbents in magnetic solid-phase extraction (MSPE). By integrating the unique properties of microporous organic networks (MONs) and magnetic nanoparticles, MMONs exhibit advantages such as designable structures, facile synthesis, diverse architectures, high specific surface area, and excellent stability, garnering widespread attention in the field of sample pretreatment. The current strategies for preparing MMONs mainly include in-situ growth, post-synthetic modification (PSM), and composite preparation. Among these, the in-situ growth method can be further categorized into direct in-situ growth, indirect in-situ growth, and co-doping methods. The direct in-situ growth method is straightforward to operate, enabling the construction of MMONs with well-defined core-shell structures. It also allows flexible control over the functionality and shell thickness of MMONs by adjusting the type and concentration of monomers, making it the most commonly used preparation method for MMONs. In contrast, the indirect in-situ growth method involves the introduction of an intermediate bridging layer, which complicates the synthesis process. However, the intermediate coating layer and the MONs shell can work synergistically to enhance the extraction efficiency of MMONs for targets. Although PSM requires additional reaction steps and poses challenges in controlling the modification rate and distribution of functional groups, it increases the variety and quantity of modifying groups and molecules, thereby expanding the application range of MMONs in MSPE. Furthermore, MMON composites can integrate the respective advantages of both MMONs and polymers, further broadening the applicability of MMONs. Therefore, each of the three methods mentioned above has its own advantages and disadvantages. Researchers can select the appropriate synthesis method based on the specific requirements of MSPE to prepare the desired MMONs. This review also provides a detailed discussion on the applications of MMONs in the MSPE of various organic pollutants, including pharmaceuticals, pesticides, endocrine-disrupting chemicals, mycotoxins, food additives, and per- and polyfluoroalkyl substances, and elucidates the extraction mechanisms (e.g. hydrophobic interaction, π-π stacking, electrostatic attraction, hydrogen-bonding interaction, ion pair interaction, fluorine-fluorine interaction, and π-CF interaction) between MMONs and analytes. In response to the current challenges of MMONs, future research should focus on the following areas: (1) Designing and expanding low-cost functional monomers to enrich the variety and quantity of existing functional monomers, providing other effective PSM methods for synthesizing functionalized MMONs, and introducing other functional composites to prepare MMON composites. (2) Developing target-oriented structural design or functionalization strategies to construct functionalized MMONs, with the aim of improving their selectivity toward specific targets. (3) Advancing other advanced characterization and mechanism investigation techniques to understand the extraction mechanisms of MMONs and guide their structural design or functionalization. In summary, this review aims to deepen the understanding of MMONs-based MSPE methods in the enrichment and detection of various organic pollutants, while offering guidance for the synthesis and application of MMONs.

, authors=Jinshuang WANG, Chengxiong YANG*, authorsList=Jinshuang WANG, Chengxiong YANG, authorCompany=null, correspAuthors=Chengxiong YANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1322594741296939577, articleId=1322594732895748653, tenantId=1146029695717560320, journalId=1283840372199657495, language=CN, title=磁性微孔有机网络材料在磁固相萃取中的研究进展, columnId=1284557502532534739, journalTitle=色谱, columnName=专论与综述, runingTitle=null, highlight=null, articleAbstract=

磁性微孔有机网络材料(MMONs)是一类新型磁固相萃取(MSPE)吸附剂,它融合了微孔有机网络材料(MONs)和磁性纳米颗粒的独特性能,具有结构可设计、合成简便、结构丰富、比表面积大和稳定性好等优点,在样品前处理领域受到广泛关注。本文系统综述了MMONs及其复合物的合成方法与功能化策略,详细探讨了磁固相萃取在药物、农药、内分泌干扰物、霉菌毒素、食品添加剂、全氟及多氟烷基物质等各类有机污染物中的应用,并阐述了MMONs与分析物之间的萃取机理。最后,对MMONs面临的挑战与发展前景进行了展望。本综述有助于深化科研人员对基于MMONs的MSPE方法用于富集和检测各类有机污染物的认识,并为MMONs的合成与应用提供一定参考。

, authors=王金爽, 杨成雄*, authorsList=王金爽, 杨成雄, authorCompany=null, correspAuthors=杨成雄, authorNote=null, correspAuthorsNote=
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Applications of MSPE based on MMONs in the detection of organic pollutants

, figureFileSmall=null, figureFileBig=null, tableContent=
MMONAnalytesLinear range/(μg/L)LODs/(μg/L)EFsRef.
Fe3O4@MON-NH2EDCs0.05‒10000.015‒0.03172‒197[14]
Co@NC-MON-2NH2EDCs0.03‒5000.009‒0.15151‒196[15]
Fe3O4@PDA@NMONEDCs0.18‒5000.055‒0.0992.6‒98.4[16]
MMON-SO3H-NH2drugs0.15‒10000.05‒4.582.1‒99.6[24]
EDA-Fe3O4@OH-COOH-MON-TEPTpesticides0.001‒0.750.00003‒0.0002294.8‒103.5[25]
MMON-SO3H@SO3Napesticides0.1‒5000.03‒0.0997.8‒99.7[26]
Fe3O4@MONpesticides0.001‒200.27‒3.1‒[27]
Fe3O4@MON-TBPM-DEBPEDCs1‒1000.03‒0.480.4‒98.8[29]
Fe3O4@FMONpesticides0.10‒10000.01‒0.0285.6‒98.0[30]
MCD-MONEDCs2.0‒10000.6‒1.087.9‒98.0[31]
Fe3O4@CD-MONEDCs2.0‒4000.5‒1.0183‒198[32]
MMON-COOH-2CONHdrugs3‒100001‒393.9‒99.4[33]
[PBA]3/4-MCD-MON-0.04pesticides0.2‒5000.05‒0.592.5‒96.1[34]
0.25 IL-MMONpesticides1.0‒10000.3‒1.394.6‒99.9[35]
Fe3O4@CD-MON-PBAdrugs0.5‒10000.1‒0.592.3‒98.0[36]
Fe3O4@MON-NH2@F7PFAS0.002‒20.00054‒0.00147‒[37]
Fe3O4@MON-NH2@CM-β-CDdrugs20‒10001.4‒2.3‒[38]
iMMONsdrugs0.0005‒0.20.00002‒0.000128500[39]
Pyr-T-DPM Me CMP‒‒‒‒[40]
Fe3O4@N-CMPpesticides0.1‒2000.3‒0.5‒[41]
Fe3O4@MON-PEI600drugs0.14‒4000.042‒0.14997.0‒98.2[42]
MMON-PANIdrugs0.2‒10000.07‒1.798.6‒99.9[43]
FMMONpesticides0.1‒10000.03‒0.0596.2‒99.7[44]
MMON-2OHpesticides‒0.00003‒0.0006‒[45]
MMON-DBB-2EDCs4‒4001.0‒3.698.8‒99.2[46]
MMON-BEDCs0.50‒12000.10‒0.15432‒482[47]
MMON-SO2NH2EDCs1‒10000.3‒1.080.3‒85.6[48]
Fe3O4@UiO-66-NH2@MONmycotoxins1‒5000.15‒0.87‒[49]
Fe3O4@MON-NH2-SO3Hmycotoxins10‒5000‒‒[50]
Fe3O4@MON-NH2-OHmycotoxins5‒25001.4‒3595[51]
), ArticleFig(id=1322594747504509530, tenantId=1146029695717560320, journalId=1283840372199657495, articleId=1322594732895748653, language=CN, label=表1, caption=

基于MMONs的磁固相萃取在有机污染物检测中的应用

, figureFileSmall=null, figureFileBig=null, tableContent=
MMONAnalytesLinear range/(μg/L)LODs/(μg/L)EFsRef.
Fe3O4@MON-NH2EDCs0.05‒10000.015‒0.03172‒197[14]
Co@NC-MON-2NH2EDCs0.03‒5000.009‒0.15151‒196[15]
Fe3O4@PDA@NMONEDCs0.18‒5000.055‒0.0992.6‒98.4[16]
MMON-SO3H-NH2drugs0.15‒10000.05‒4.582.1‒99.6[24]
EDA-Fe3O4@OH-COOH-MON-TEPTpesticides0.001‒0.750.00003‒0.0002294.8‒103.5[25]
MMON-SO3H@SO3Napesticides0.1‒5000.03‒0.0997.8‒99.7[26]
Fe3O4@MONpesticides0.001‒200.27‒3.1‒[27]
Fe3O4@MON-TBPM-DEBPEDCs1‒1000.03‒0.480.4‒98.8[29]
Fe3O4@FMONpesticides0.10‒10000.01‒0.0285.6‒98.0[30]
MCD-MONEDCs2.0‒10000.6‒1.087.9‒98.0[31]
Fe3O4@CD-MONEDCs2.0‒4000.5‒1.0183‒198[32]
MMON-COOH-2CONHdrugs3‒100001‒393.9‒99.4[33]
[PBA]3/4-MCD-MON-0.04pesticides0.2‒5000.05‒0.592.5‒96.1[34]
0.25 IL-MMONpesticides1.0‒10000.3‒1.394.6‒99.9[35]
Fe3O4@CD-MON-PBAdrugs0.5‒10000.1‒0.592.3‒98.0[36]
Fe3O4@MON-NH2@F7PFAS0.002‒20.00054‒0.00147‒[37]
Fe3O4@MON-NH2@CM-β-CDdrugs20‒10001.4‒2.3‒[38]
iMMONsdrugs0.0005‒0.20.00002‒0.000128500[39]
Pyr-T-DPM Me CMP‒‒‒‒[40]
Fe3O4@N-CMPpesticides0.1‒2000.3‒0.5‒[41]
Fe3O4@MON-PEI600drugs0.14‒4000.042‒0.14997.0‒98.2[42]
MMON-PANIdrugs0.2‒10000.07‒1.798.6‒99.9[43]
FMMONpesticides0.1‒10000.03‒0.0596.2‒99.7[44]
MMON-2OHpesticides‒0.00003‒0.0006‒[45]
MMON-DBB-2EDCs4‒4001.0‒3.698.8‒99.2[46]
MMON-BEDCs0.50‒12000.10‒0.15432‒482[47]
MMON-SO2NH2EDCs1‒10000.3‒1.080.3‒85.6[48]
Fe3O4@UiO-66-NH2@MONmycotoxins1‒5000.15‒0.87‒[49]
Fe3O4@MON-NH2-SO3Hmycotoxins10‒5000‒‒[50]
Fe3O4@MON-NH2-OHmycotoxins5‒25001.4‒3595[51]
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磁性微孔有机网络材料在磁固相萃取中的研究进展
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王金爽 , 杨成雄 *
色谱 | 专论与综述 2026,44(10): 1175-1189
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色谱 |专论与综述 2026 , 44 (10) : 1175 -1189
磁性微孔有机网络材料在磁固相萃取中的研究进展
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王金爽, 杨成雄*
作者信息
  • 1山东第一医科大学药学院(药物研究所), 山东 济南 250117
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Research progress of magnetic microporous organic networks in magnetic solid-phase extraction
Jinshuang WANG, Chengxiong YANG*
Affiliations
  • 1School of Pharmaceutical Sciences & Institute of Materia Medica, Shandong First Medical University, Jinan 250117, China
出版时间: 2026-10-08 doi: 10.3724/SP.J.1123.2025.12010
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磁性微孔有机网络材料(MMONs)是一类新型磁固相萃取(MSPE)吸附剂,它融合了微孔有机网络材料(MONs)和磁性纳米颗粒的独特性能,具有结构可设计、合成简便、结构丰富、比表面积大和稳定性好等优点,在样品前处理领域受到广泛关注。本文系统综述了MMONs及其复合物的合成方法与功能化策略,详细探讨了磁固相萃取在药物、农药、内分泌干扰物、霉菌毒素、食品添加剂、全氟及多氟烷基物质等各类有机污染物中的应用,并阐述了MMONs与分析物之间的萃取机理。最后,对MMONs面临的挑战与发展前景进行了展望。本综述有助于深化科研人员对基于MMONs的MSPE方法用于富集和检测各类有机污染物的认识,并为MMONs的合成与应用提供一定参考。

磁性微孔有机网络  /  磁固相萃取  /  样品前处理  /  有机污染物

Recently, magnetic microporous organic networks (MMONs) have emerged as a novel class of adsorbents in magnetic solid-phase extraction (MSPE). By integrating the unique properties of microporous organic networks (MONs) and magnetic nanoparticles, MMONs exhibit advantages such as designable structures, facile synthesis, diverse architectures, high specific surface area, and excellent stability, garnering widespread attention in the field of sample pretreatment. The current strategies for preparing MMONs mainly include in-situ growth, post-synthetic modification (PSM), and composite preparation. Among these, the in-situ growth method can be further categorized into direct in-situ growth, indirect in-situ growth, and co-doping methods. The direct in-situ growth method is straightforward to operate, enabling the construction of MMONs with well-defined core-shell structures. It also allows flexible control over the functionality and shell thickness of MMONs by adjusting the type and concentration of monomers, making it the most commonly used preparation method for MMONs. In contrast, the indirect in-situ growth method involves the introduction of an intermediate bridging layer, which complicates the synthesis process. However, the intermediate coating layer and the MONs shell can work synergistically to enhance the extraction efficiency of MMONs for targets. Although PSM requires additional reaction steps and poses challenges in controlling the modification rate and distribution of functional groups, it increases the variety and quantity of modifying groups and molecules, thereby expanding the application range of MMONs in MSPE. Furthermore, MMON composites can integrate the respective advantages of both MMONs and polymers, further broadening the applicability of MMONs. Therefore, each of the three methods mentioned above has its own advantages and disadvantages. Researchers can select the appropriate synthesis method based on the specific requirements of MSPE to prepare the desired MMONs. This review also provides a detailed discussion on the applications of MMONs in the MSPE of various organic pollutants, including pharmaceuticals, pesticides, endocrine-disrupting chemicals, mycotoxins, food additives, and per- and polyfluoroalkyl substances, and elucidates the extraction mechanisms (e.g. hydrophobic interaction, π-π stacking, electrostatic attraction, hydrogen-bonding interaction, ion pair interaction, fluorine-fluorine interaction, and π-CF interaction) between MMONs and analytes. In response to the current challenges of MMONs, future research should focus on the following areas: (1) Designing and expanding low-cost functional monomers to enrich the variety and quantity of existing functional monomers, providing other effective PSM methods for synthesizing functionalized MMONs, and introducing other functional composites to prepare MMON composites. (2) Developing target-oriented structural design or functionalization strategies to construct functionalized MMONs, with the aim of improving their selectivity toward specific targets. (3) Advancing other advanced characterization and mechanism investigation techniques to understand the extraction mechanisms of MMONs and guide their structural design or functionalization. In summary, this review aims to deepen the understanding of MMONs-based MSPE methods in the enrichment and detection of various organic pollutants, while offering guidance for the synthesis and application of MMONs.

magnetic microporous organic network (MMON)  /  magnetic solid-phase extraction (MSPE)  /  sample pretreatment  /  organic pollutant
王金爽, 杨成雄. 磁性微孔有机网络材料在磁固相萃取中的研究进展. 色谱, 2026 , 44 (10) : 1175 -1189 . DOI: 10.3724/SP.J.1123.2025.12010
Jinshuang WANG, Chengxiong YANG. Research progress of magnetic microporous organic networks in magnetic solid-phase extraction[J]. Chinese Journal of Chromatography, 2026 , 44 (10) : 1175 -1189 . DOI: 10.3724/SP.J.1123.2025.12010
微孔有机网络材料(MONs)是一类通过炔代芳烃与卤代芳烃之间的Sonogashira-Hagihara偶联反应合成的新型多孔材料[1-5]。因其结构可设计、合成简便、种类多样、比表面积大、溶剂和热稳定性好,以及孔隙和功能可调等特点[6,7],近年来MONs在污染物去除[8-13]、样品前处理[14-16]、色谱分离[17-23]等领域受到广泛关注。此外,MONs易与其他基质材料复合,可通过原位生长法、后修饰法(PSM)和制备复合物法等便捷地将其修饰于磁性纳米颗粒(MNPs)表面,从而制备磁性MONs(MMONs)[24-26]。MMONs结合了MNPs的易分离特性与MONs优异的吸附性能,在磁固相萃取(MSPE)中日益受到重视。自2018年Li课题组[27]报道将MMONs用于MSPE以来,科研人员设计并合成了一系列功能化MMONs,并将其应用于富集和检测水体、土壤、食品和生物样品等复杂基质中的各类有机污染物,如农药、抗生素、非甾体抗炎药物(NSAIDs)、抗癫痫药、雌激素、内分泌干扰物(EDCs)、多环芳烃(PAHs)、植物生长调节剂(PGRs)、生物毒素、食品添加剂以及全氟和多氟烷基物质(PFASs)等。鉴于MMONs在MSPE领域的快速发展,对其研究进展进行总结和评述十分必要。然而,目前仍缺乏系统评述MMONs在MSPE中研究进展的综述。虽然2023年余涛等[28]发表了相关的综述,但由于当时MMONs在MSPE中的应用仍处于起步阶段,文中有关MMONs的制备方法和类型及其MSPE应用等内容叙述较少。
为此,本综述系统总结了MMONs在MSPE中的最新进展与应用,介绍了MMONs的制备方法、策略与分类,阐述了其作为高效吸附剂在环境、食品及生物样品中的MSPE应用,并对其面临的挑战与前景进行了展望。
根据MMONs功能、形貌及应用需求,目前用于制备MMONs的方法主要包括原位生长法、PSM和制备复合物法3种(图1)。其中原位生长法又可分为直接原位生长法、间接原位生长法和共掺杂法。此外,鉴于MMONs的组成与功能基团种类,MMONs又可分为未功能化MMONs、功能化MMONs和MMONs复合物。未功能化MMONs仅包含MNPs和MONs两种组分,通过将不含官能团的MONs负载于MNPs上制备而成。而功能化MMONs同样包含MNPs和MONs两部分,但功能化MMONs是通过使用功能单体原位生长合成、功能小分子掺杂或PSM获得。MMONs复合物则包含MNPs、MONs以及其他组分(如其他多孔材料与聚合物等)。
原位生长法是制备MMONs最常用的方法。该方法以MNPs为模板与磁核,通过直接、间接或共掺杂的方式将MONs负载于MNPs表面制备MMONs[14]。直接与间接原位生长法的区别在于是否引入中间包覆层,常用的包覆层包括硅烷化试剂如正硅酸乙酯、丙基三甲氧基硅烷(GLYMO)或聚多巴胺(PDA)等[16,27],而共掺杂法则是在直接原位生长法的基础上除了加入必须的炔基和卤代单体之外,还需要加入另一功能性炔代或卤代小分子。
直接原位生长法如其名所示,是将MON有机单体直接聚合于MNPs表面获得MMONs。例如,Ali等[29]以四(4-溴苯基)甲烷(TBPT)和4,4′-二乙炔基联苯(TEB)为单体采用直接原位生长法合成了Fe3O4@MON-TBPT-TEB。该吸附剂具有丰富的π-π和疏水相互作用位点,在25 ℃下对2,4,6-三氯酚(TCP)的吸附量高达440 mg/g。建立了其MSPE-HPLC-UV检测TCP方法,检出限为0.03 μg/L,定量限为0.11 μg/L,线性范围为1~1 000 μg/L,揭示了MMONs材料在MSPE领域良好的应用潜力。
上述MMONs由未功能化的TBPT和TEB单体构建,具有丰富的共轭芳香结构和超疏水性,能为芳香族及疏水性目标物提供较强的π-π与疏水作用力,但对极性环境污染物的富集性能仍有很大的提升空间。因此,非常有必要在MON骨架中引入额外的极性官能团或其他基质,以提高其选择性及灵敏度,拓展其适用范围,尤其是极性目标物。因此,选择含有功能基团的单体通过直接原位生长法可以构建含有单一或多个官能团的功能化MMONs。该方法的优势在于功能化基团密度高、分布均匀且合成简便。目前,已报道的官能团包括氨基、羟基、羧基、磺酸基、酰氨基、氟原子、三嗪环、环糊精(CD)和离子液体(IL)等。例如,Du等[14]通过直接原位生长法制备了具有均匀核-壳结构的磁性氨基功能化MON(Fe3O4@MON-NH2)(图1a-Ⅰ)。将Fe3O4、催化剂Pd(PPh3)2Cl2和CuI与溶剂三乙胺和甲苯混合,再加入单体四(4-乙炔基苯基)甲烷(TEPM)和2,5-二溴苯胺,在90 ℃下反应5 h得最终产物。随后,对比了Fe3O4、Fe3O4@MON和Fe3O4@MON-NH2对极性EDCs的萃取性能。Fe3O4对4种EDCs的富集因子为12~23,Fe3O4@MON的为125~138,而引入-NH2后,Fe3O4@MON的富集因子继续增至172~197,证明了在MONs骨架中引入合适的官能团能显著提升其富集和萃取性能。除了以磁性Fe3O4为核外,本课题组还以2,5-二溴苯-1,4-二胺为功能单体,以磁性Co与N掺杂多孔碳(Co@NC)为核合成了一种新颖的氨基MMONs(Co@NC-MON-2NH2)用于MSPE果蔬中的PGRs[15]。氨基的修饰有效增加了Co@NC-MON-2NH2的氢键结合位点,从而提升了对极性PGRs的富集性能。同时,该方法还可拓展至含有不同氨基的MMONs如Co@NC-MON和Co@NC-MON-NH2的合成,具有良好的普适性。值得注意的是,含有钴元素的ZIF-67经煅烧所得的Co@NC不仅可作为磁分离核和MON-2NH2生长的载体,其结构中所含的多孔石墨碳可进一步提升对PGRs的萃取效率,为功能化MMONs的制备提供了新的载体和介质。
除了氨基以外,通过选择氟功能化的单体也能引入特异性的F-F和C-F…π结合位点,从而提高MMONs对含氟目标物的选择性和富集效率。为此,本课题组以1,4-二溴四氟苯为氟化单体通过简便的直接原位生长法合成了一种新型的Fe3O4@FMON吸附剂,用于萃取苯甲酰脲类杀虫剂(BUs)[30]。由于大量氟原子的引入,Fe3O4@FMON对含氟BUs具有优异的选择性,其萃取效率远高于其他不含氟的目标物(香兰素类、双酚类、OH-PAHs等)。
将CD单体直接引入MONs骨架是构建功能化MMONs的另一途径。同时,CD单体的疏水内腔与亲水外层可进一步增加MMONs的功能位点,为极性分析物提供额外的氢键作用与主客体相互作用位点,赋予MMONs独特性质,可有效拓展MMONs的应用范围。例如,本课题组系统研究了直接原位生长法合成多种新型CD基MMONs(Fe3O4@CD-MONs)[31,32],并通过优化单体拓扑结构、单体浓度和反应溶剂种类实现了对其形貌与壳层厚度的调控。结果发现,选择线性芳香炔单体有利于形成片状CD-MMONs,而选用非线性芳香炔则易形成核-壳结构的Fe3O4@CD-MON。此外,通过调控合成核-壳结构的Fe3O4@CD-MON条件,可以将单体消耗量减少至片状CD-MMONs的1/10,在保障萃取效率的同时可大大降低Fe3O4@CD-MON的合成成本。
上述研究表明在MMONs结构中引入适当的官能团可有效增加其萃取性能,但仅选用了含单一官能团如-NH2、-F及CD等的单体,其萃取性能仍有待进一步提升。为实现这一目标,研究人员将多种官能团同时引入MONs骨架以提供更多的协同作用位点。例如,Li等[24]以同时含有-NH2与-SO3H 2种官能团的2,5-二氯苯胺磺酸为单体,通过直接原位生长法合成了一种新型的两性离子MMONs(MMON-SO3H-NH2)。所得吸附剂具有高比表面积(359.5 m2/g)、快速磁响应性(39.43 emu/g)、良好稳定性(重复使用次数>20次)和多重结合位点(芳环、-SO3H和-NH2),可实现对两性离子型抗生素的高效萃取。MMON-SO3H-NH2结构中由于同时引入了-NH2和-SO3H 2种官能团,其萃取回收率高于单一功能化的MMONs(MMON-SO3H和MMON-NH2),证明了多功能化是提升MMONs萃取性能的有效方法。近期,Li等[33]还报道了直接原位生长法合成另一新型功能化MMON(MMON-COOH-2CONH),由于一个单体结构中含有一个-COOH和两个-CONH基团,对头孢菌素类(CEFs)具有优异的萃取效果,其富集倍数高达93.9~99.4,接近于理论上的最大值100,最终成功用于检测山羊、牛和骆驼奶粉样品中的CEFs。
与直接原位生长法不同,间接原位生长法需先使用包覆剂对MNPs进行修饰,再将MON负载于MNPs表面。例如,Lei等[27]通过该方法制备了Fe3O4@MON。首先通过Fe3O4@SiO2与GLYMO的硅烷化反应得到Fe3O4@SiO2-GLYMO,再通过缩合反应将炔基单体氨基苯乙炔(APE)引入合成Fe3O4@SiO2-APE,最后加入1,3,5-三溴苯与1,3,5-三乙炔基苯(TBE)单体获得最终产物Fe3O4@MON。该方法不仅能精确实现MONs在MNPs上的原位聚合,还可赋予MMONs优异的溶剂和热稳定性。2021年,He等[16]以PDA为包覆剂,通过间接原位生长法制备了Fe3O4@PDA@NMON(图1a-Ⅱ)。PDA包覆层的引入不仅能有效防止Fe3O4团聚和氧化,还可通过结构中的苯环、-OH和-NH2协同提升Fe3O4@PDA@NMON对羟基PAHs(OH-PAHs)和对硝基苯酚的萃取性能。
共掺杂法则是为了解决现有MONs合成单体种类和数量有限以及单体价格昂贵的问题,在直接原位生长法的基础上加入另一功能炔基或卤代小分子合成功能化MMONs的方法。例如,Xu等[34]以七(6-碘-6-脱氧)-β-CD(7-I-β-CD)和1,3,5-三(4-乙炔基苯基)苯(TEPB)为单体,以含有硼酸基团的(4-乙炔基苯基)硼酸(EPBA)为炔基小分子,首次采用一锅共掺杂法合成了苯硼酸(PBA)功能化的MMONs([PBA]3/4-MCD-MON-0.04)(图1a-Ⅲ)。作者详细研究了TEPB与EPBA掺杂比例和单体浓度对其形貌、壳层厚度、性能及萃取效率的影响,为合成新型功能化MMONs提供了新策略。除了炔基小分子外,卤代小分子也可用于掺杂合成功能化MMONs。最近,Li等[35]采用该掺杂策略,以溴化离子液体2-溴乙基三甲基溴化铵作为功能分子,与TEPM和1,4-二溴苯发生原位偶联反应成功合成了IL-MMONs。该材料由于在结构上引入了季铵型IL,显著增强了其亲水性,并能在较宽的pH范围内保持正电性,从而大大增加了对强极性苯氧羧酸类除草剂(PCAs)的亲和力。同时,通过调节IL掺杂比例可对其萃取性能进行调控。上述结果表明,通过调控嵌入MONs骨架的炔基或卤代小分子的类型与比例,能够精确调控其表面电荷特性,进而改善材料富集极性分子的能力,充分体现了MMONs在结构与功能设计方面的高度可调性与可设计性。
上述研究表明,原位生长法简便、高效,且作用位点与官能团能均匀分布于MMONs骨架中。此外,可根据分析物的结构特征精确设计MMONs,是目前最常用的MMONs合成方法。然而,功能单体种类和数量的有限性在一定程度上限制了其适用性。为解决这一问题,PSM应运而生。与原位生长法不同,PSM则需先合成MMONs,再通过共价反应将官能团或功能分子引入MMONs骨架中。常用的化学反应包括巯基-炔“点击”反应、酰胺化反应与Menschutkin(门舒特金)反应。
由于MONs骨架中富含炔基,巯基-炔“点击”PSM策略成为制备多功能MMONs的首选和有效方法。2021年,He等[26]根据苯并咪唑类杀菌剂(BZDs)结构中含有苯环、咪唑环和酰基氨基的特点,报道了巯基-炔“点击”反应PSM合成富含磺酸基MMONs(MMON-SO3H@SO3Na)的研究(图1b)。由于通过单体和PSM在MMON结构中引入了大量的磺酸基团,所得吸附剂表现出优异的亲水性,在水溶液中具有良好的分散性,可在MSPE过程中与BZDs充分接触。同时,该吸附剂可为极性BZDs提供丰富的静电吸引、离子交换、π-π作用及氢键位点,协同提升萃取性能。此外,Xu等[36]通过巯基-炔“点击”反应将PBA引入CD-MON骨架中,制备了PBA功能化的CD-MMON(Fe3O4@CD-MON-PBA)。引入的PBA分子增强了Fe3O4@CD-MON的亲水性,并提供了特异性的B-N配位结合位点,实现了含氮目标物的选择性萃取。上述结果表明,通过巯基-炔“点击”PSM策略引入官能团或功能分子,可便捷地制备功能化MMONs,利于其在MSPE中的应用。
酰胺化反应(亦称N-酰化反应)指胺与酰基化合物在特定条件下发生的反应,如通过小分子缩合(如芳胺与羧酸或酰氯的缩合)形成酰胺化合物。此类反应也可用于PSM制备功能化MMONs。例如,Zhang课题组[37]以Fe3O4、TBE和2,5-二溴苯胺为原料,采用直接原位生长法先合成了Fe3O4@MON-NH2,再在N2保护条件下通过N-酰化反应将多氟烷基酰氯链接枝到氨基功能化的Fe3O4@MON-NH2上,制备了富含氟原子的新型磁性吸附剂Fe3O4@MON-NH2@F7。该萃取剂具有高比表面积、良好疏水性及丰富氟基团,能通过静电吸引、疏水作用、F-F相互作用、π-CF作用及氢键作用实现对PFAS的高效、高选择性萃取。基于相似思路,Cui等[38]通过芳胺与羧基的缩合反应,制备了一种对氟喹诺酮类抗生素(FQs)具有优异吸附性能的羧甲基CD修饰的磁性氨基MONs(Fe3O4@MON-NH2@CM-β-CD)。
门舒特金反应是一种叔胺与卤代烃发生亲核取代形成季铵盐的经典反应,为构建功能化MMONs提供了另一PSM途径。例如,Ge等[39]以2,5-二溴嘧啶为构筑单元合成了含三嗪单元的中性MONs,随后通过碘甲烷对嘧啶进行PSM季铵化,最终获得阳离子型MMONs。该PSM过程不仅在MONs骨架中形成了季铵基团,还有效地引入了介孔通道。凭借其分级微-介孔结构、阳离子骨架及π共轭主链,该MMONs表现出对喹诺酮类抗生素(QAs)优异的吸附性能和可重复使用性。基于此,发展了复杂样品中基于该萃取剂的MSPE-HPLC-MS/MS检测方法,并通过吸附实验、密度泛函理论计算及系统材料表征,深入探究了其吸附机理。与此同时,Kuo课题组[40]通过碘甲烷与芘基MON前体间的门舒特金 PSM反应,制备了阳离子型MMONs材料。相较于母体MONs,所制备的吸附剂对金黄色葡萄球菌展现出显著增强的杀菌活性,凸显了修饰后的季铵基团在抗菌中的关键作用。最近,Xia等[41]报道了一种改进型PSM方法用于合成季铵MMONs(Fe3O4@N-CMP)。以TBE与1,4-二溴-2,5-双(溴乙基)苯为构筑单元,以Fe3O4为磁核,通过Sonogashira-Hagihara偶联合成Fe3O4@N-CMP。在Fe3O4@N-CMP合成过程中,三乙胺不仅作为反应溶剂,也可作为功能分子与苄基溴发生季铵化反应将季铵基团引入MON骨架中,赋予最终产物季铵特性。多种表征手段证实了Fe3O4@N-CMP的成功合成与季铵化。所合成的吸附剂具有高比表面积、良好的化学稳定性、丰富的离子基团及较强的新烟碱类杀虫剂(NEOs)吸附亲和力。
上述研究表明,巯基-炔“点击”PSM反应高效且特异性强,但通常需要加热、惰性气体保护及较长反应时间。相比之下,酰胺化反应和季铵化反应的条件较温和便捷。然而,目前季铵化与酰胺化反应仍受限于MONs骨架中存在的特定基团。因此,探索并设计更多的PSM反应用于制备功能化MMONs对拓展其MSPE应用至关重要。
MMONs复合物由MMONs与其他聚合物结合形成,能综合MMONs与聚合物各自的优点,提升其对目标物的富集效率,是构建功能化MMONs的另一有效途径。目前用于制备MMONs复合物的聚合物包括富含氨基的水溶性聚乙烯亚胺(PEI)与聚苯胺(PANI)。2021年,本课题组[42]报道通过将PEI600包覆于磁性Fe3O4@MON表面,制备了PEI600修饰的MMONs复合物(Fe3O4@MON-PEI600)。详细考察了PEI相对分子质量(600、1 800和10 000)和浓度对其萃取性能的影响。PEI的修饰不仅增强了Fe3O4@MON-PEI600的极性与分散性,还因结构中含有丰富的氢键与静电吸引位点提升了对NSAIDs的萃取效率。近期,我们还合成了一种新型PANI包覆的MMONs(MMON-PANI)用于MSPE和检测鸡肉、牛肉和猪肉样品中的NSAIDs[43](图1c)。该吸附剂融合了Fe3O4、MON与PANI各自的优势,可提供高比表面积、快速磁响应、良好稳定性及多重结合位点,证明了在MMON结构中掺入PANI是提高NSAIDs富集效率的有效途径,为合成功能化MMONs复合物及促进其样品前处理应用提供了新的策略。上述两种制备功能化MMONs复合物的策略还表现出合成条件温和与可重复使用性好的优点,有望拓展MMON复合物在MSPE中的应用。
综上所述,直接原位生长法操作简便,能构建形貌规整的核-壳结构MMONs,且可通过调节单体种类和浓度灵活调控MMONs的功能和壳层厚度,是目前最常用的MMONs制备方法。相比之下,间接原位生长法因需引入中间桥连层而导致合成过程更为复杂,但中间包覆层与MONs壳层可协同提升MMONs对目标物的萃取效率。但是,原位生长法可用单体数量和种类有限,导致其应用受限。然而,该限制可以通过PSM解决。虽然PSM需要额外的反应步骤,且修饰率和功能基团的分布难以调控,但它增加了修饰基团和分子的数量以及应用范围。此外,MMONs复合物能整合MMONs与聚合物各自的优点,可进一步拓宽MMONs的适用范围。因此,上述3种方法各有利弊,研究者可根据MSPE的具体需求选择合适的合成方法制备目标MMONs。
2018年,Li课题组[27]报道了利用磁性Fe3O4@MON磁固相萃取果蔬中6种杀菌剂。该材料通过疏水作用与π-π相互作用实现了痕量杀菌剂的快速分离、回收与富集。所建立的方法检出限低(0.27~3.1 μg/L)、线性范围宽(0.001~20 μg/L),并能有效减少基质干扰,保证结果准确性。随后,人们设计并合成了一系列不同功能化的MMONs,并成功用于食品、环境及生物样品中各类痕量农药、药物、EDCs、真菌毒素、PFASs及其他污染物的高效富集与检测(表1)。
除草剂、杀菌剂、杀虫剂等农药的过度或非法使用导致严重的环境污染与食品安全问题,开发简便、快速、可靠且灵敏度高的检测技术,用于分析复杂食品与环境样品中的痕量农药残留具有重要意义。
BZDs如奥芬达唑和噻苯达唑,是广泛应用于农产品采收前后预防真菌病害的农药,其残留对人类健康构成潜在风险。本课题组通过含磺酸基单体与巯基-炔“点击”PSM相结合,以3-巯基-1-丙磺酸钠为修饰剂,合成了一种新型的富含磺酸基的萃取剂MMON-SO3H@SO3Na,用于复杂食品基质中BZDs的高效MSPE与HPLC检测[26]。基于预设的针对BZDs的多重离子交换、氢键及π-π作用位点,所开发的基于MMON-SO3H@SO3Na的MSPE-HPLC方法具有检出限低(0.03~0.09 μg/L)、线性范围宽(0.1~500 μg/L)、富集因子高(97.8~99.7)及精密度好(RSD,0.8%~4.8%)等优点,成功用于黄瓜、西红柿和梨样品中BZDs的检测。为了证明MON骨架和磺酸基团的作用,作者比较了Fe3O4、MMON、MMON-SO3H和MMON-SO3H@SO3Na 4种萃取剂的富集因子。其中未经功能化的Fe3O4仅为13.8~28.2,经表面修饰MON后,MMON对BZDs的富集因子提升至70.7~77.5,证明了MON骨架提供的π-π作用位点在萃取过程中占主导作用。而MMON-SO3H对BZDs的富集因子为76.4~82.9,证明了磺酸基团对提升BZDs萃取效率的积极作用。进一步经过PSM引入磺酸基团,MMON-SO3H@SO3Na对BZDs富集因子继续提升至97.8~99.7,充分证明了磺酸基团对提升BZDs萃取效率的协同作用。该工作为构建多功能MMONs以及富集复杂基质中痕量BZDs提供了新的PSM策略。
NEOs因其高效、低剂量、广谱杀虫及低成本等优点而广泛用于害虫防治。然而,NEOs水溶性好,在自然地表水中可快速扩散,并在食品样品中残留,对人类健康构成风险。Xia等[41]报道了一种季铵基团功能化的MMONs(Fe3O4@N-CMP),所发展的策略通过巧妙选取同时含溴代芳烃与苄溴结构的功能单体,在Sonogashira-Hagihara偶联反应过程中,同步完成三乙胺与苄溴位点间的季铵化反应,从而将正电性的季铵基团直接、稳定地锚定在MONs骨架中。得益于大的比表面积、丰富的π-π堆积、路易斯酸碱作用及静电相互作用位点,Fe3O4@N-CMP对NEOs表现出高吸附容量与萃取效率。该材料也表现出优异的可重复使用性,经过10次萃取-解吸循环后其回收率仍可保持95%以上。最终,所建立的样品前处理方法成功用于自来水、雨水及湖水样品中NEOs的检测分析,加标回收率为70.4%~122.7%。
BUs通过干扰几丁质合成导致害虫死亡或不育,其结构具有苯甲酰基团与高氟含量等特征。为此,本课题组[30]选用含氟功能单体,采用直接原位生长法在磁性Fe3O4表面一步构建了一种新型的氟化Fe3O4@FMON(图2)。该设计针对BUs分子兼具苯甲酰基团和高氟含量的结构特点,使材料不仅通过芳香骨架提供π-π相互作用,更通过引入的氟原子产生特异性F-F相互作用,同时增强材料的疏水性和化学稳定性。这一设计使Fe3O4@FMON对BUs表现出优异的吸附能力,在复杂茶饮料基质中实现了痕量BUs的高效萃取。所发展的方法线性范围宽(0.10~1 000 μg/L),检出限低(0.01~0.02 μg/L)、富集因子高(85.6~98.0)、重复使用性好(至少8次)和抗干扰能力好(基质效应为88.6%~113.8%)。此外,该吸附剂对BUs的富集因子明显高于其他非含氟目标物,揭示了F-F相互作用在选择性萃取BUs中的重要贡献。同时,Fe3O4@FMON在8次萃取-解吸循环后其回收率只下降了2.3%~5.4%,且重复使用后的吸附剂形貌和结构与新制备的无明显差别,表明其良好的可重复使用性和稳定性。该工作证明了Fe3O4@FMON富集复杂基质中痕量BUs的良好前景,揭示了FMON用于富集氟化分析物的潜力。
苯基吡唑类杀虫剂(PPIs)广泛用于蔬菜、水稻等作物害虫的防治,是农业生产中最常用的杀虫剂之一,它通过影响昆虫体内γ-氨基丁酸控制的氯离子通道,干扰昆虫中枢神经系统功能,最终导致昆虫死亡。氟虫腈和乙虫腈是2种最常用的PPIs。研究表明,长期摄入被PPIs污染的食物会损害动物的肝肾功能。因此,PPIs残留带来的环境和健康风险不容忽视。为此,基于氟虫腈和乙虫腈的强疏水及含氟特性,Kang等[44]选择了含氟原子更多的4,4′-二溴八氟联苯为反应单体,采用直接原位生长法制备了一种新型的富氟磁性萃取剂FMMON,用于高效、高选择性MSPE牛奶和鸡蛋样品中的氟虫腈和乙虫腈。该吸附剂具有比表面积大(232.9 m2/g)、作用位点多(F-F、氢键、疏水和π-π)和磁分离性能与稳定性好的优点。在最佳萃取条件下,所建立的富集和检测方法对氟虫腈和乙虫腈的线性范围为0.1~1 000 μg/L、检出限为0.03~0.05 μg/L、富集因子为96.2~99.7(理论最大值为100)、吸附剂用量仅为4 mg,萃取时间为6 min。对比了Fe3O4@FMON[30]、MMON和FMMON对氟虫腈和乙虫腈的萃取回收率,结果表明富氟的FMMON回收率明显高于不含氟的MMON,揭示了氟原子在萃取氟虫腈和乙虫腈过程中的重要作用。同时,以4,4′-二溴八氟联苯为单体合成的FMMON的萃取效率优于1,4-二溴四氟苯为单体合成的Fe3O4@FMON[30],进一步证明了F-F相互作用的重要性以及在MMON骨架中引入更多的氟原子有利于提升其对氟虫腈和乙虫腈的吸附和萃取性能。
苯脲类除草剂(PUHs)是一类通过抑制光合作用控制一年生与多年生杂草的高效广谱除草剂。由于其高生态毒性及缓慢的生物降解性,PUHs残留的潜在生物与环境危害十分显著。因此,Liu等[25]将预先独立合成的功能单体通过共价键进行整合,制备了用于萃取PUHs的磁性吸附剂。首先分别合成氨基功能化的Fe3O4(EDA-Fe₃O₄)和羧基功能化的羟基MON(OH-COOH-MON-TEPT),随后利用EDC-NHS介导的酰胺化反应将EDA-Fe3O4与OH-COOH-MON-TEPT共价连接,最终形成具有明确结构的双功能化MMONs复合物。该策略的优势在于能够有效保留各组分的原始特性,并通过可控的组装过程实现功能的集成与结构的精准调控。所合成的磁性吸附剂具有大量的π-π、氢键和卤键位点,可以有效捕获环境水和果汁样品中的PUHs。
PCAs是一类广泛应用于阔叶杂草防治的重要除草剂。因其成本低廉、选择性强且除草效率高,PCAs在农作物种植中得到了广泛使用。PCAs具有较强的极性和良好的水溶性,易通过多种途径流入地表水和地下水。长期接触或摄入PCAs可能引发发热、肌肉无力、腹痛、低血压、肝脏损伤等一系列中毒症状,甚至存在致癌风险。因此,开发高效、选择性好、灵敏度高的检测方法,用于准确检测与分析农产品中的痕量PCAs残留具有重要意义。最近,Li等[35]通过原位掺杂策略,设计并合成了新型的IL功能化的MMONs(IL-MMONs)(图3),用于MSPE富集和检测蔬菜样品中4种PCAs。通过在TEPM与1,4-二溴苯偶联反应前,将溴化IL单体2-溴乙基三甲基溴化铵成功掺入MMONs骨架中,经精确调控IL在MMONs中的掺杂比例,最终得到具有核-壳结构的0.25 IL-MMONs。该吸附剂富含静电吸引、离子交换及π-π相互作用位点,对PCAs展现出高的回收率。同时,所提出的IL-MMONs合成策略具有较好的可重复性。通过系统优化MSPE影响因素,并结合实验与密度泛函理论(DFT)计算,阐明了0.25 IL-MMONs对PCAs的萃取机理。本研究表明,IL功能化可提升MMONs对复杂样品中痕量、极性及离子型PCAs的萃取性能,为合成IL-MMONs提供了新策略,并为IL-MMONs的样品前处理应用奠定了基础。
磺酰脲类除草剂(SUHs)是一类高效低毒的除草剂,由芳香环、酰脲桥及具有抑制植物乙酰羟酸合成活性的含氮芳杂环三部分组成。鉴于上述SUHs的结构特征,本课题组通过简便的一锅原位掺杂策略合成了PBA功能化的[PBA]3/4-MCD-MON-0.04,用于高选择性萃取复杂食品及环境水样中的SUHs[34]。[PBA]3/4-MCD-MON-0.04提供了协同的氢键作用、主客体作用、疏水作用、特异性B-N配位及π-π作用位点,实现了多种实际样品中SUHs的灵敏、选择性检测。[PBA]3/4-MCD-MON-0.04对所研究的3种SUHs的吸附量高达140.0~269.5 mg/g,所发展的MSPE-HPLC-UV方法的检出限为0.05~0.5 μg/L,低于或与基于TpBD-(NH2)2@Fe3O4、AL-MoS2@Fe3O4、Fe3O4@PDA-DES、MIPs、Nd2Fe14B/UIO-66(Zr)-NH2和MGO@PDA-MIPs等吸附剂的方法相当。通过对比实验、红外吸收光谱、X-射线光电子能谱等手段证明了B-N配位作用在提升萃取效率和选择性中的重要贡献。本工作提出的一锅原位掺杂策略重现性好、掺杂量可调控、掺杂分子也可替换,是一种普适性的方法,可为合成新型多功能磁性CD-MONs基吸附剂提供新思路。所制备的功能化CD-MONs可综合CD、MONs和掺杂分子的优点和作用位点,在样品前处理中具有良好的应用潜力。
三嗪类除草剂(THs)广泛用于防除各类禾本科与阔叶杂草。然而,其在施用后易在水体、土壤及农产品中残留,可引发“致癌、致畸、致突变”三重毒性效应,并导致内分泌干扰及其他不可逆的副作用。针对该类化合物结构中普遍存在的-Cl、-NH-及苯环基团,Zhang等[45]近期报道了一种基于MMON-2OH的新型富集检测方法。首先通过Sonogashira-Hagihara偶联反应在室温下合成了富含羟基的MON-2OH,随后与羧基修饰的Fe3O4共价偶联合成了MMON-2OH复合物。所制得的MMON-2OH具有高比表面积(287.86 m2/g)、良好的超顺磁性(饱和磁化强度33.24 emu/g),其表面长链羟基、三嗪环及芳香骨架可提供多重作用位点,能够通过氢键(N-H…O、O-H…N)、卤键(Cl…N)及π-堆积(NH-π、CH-π、π-π)等机制与THs分子结合,从而实现高效吸附与快速磁分离。所发展的方法检测水样和蜂蜜中THs的线性范围分别为1~2 000 ng/L和0.08~160 μg/kg,检出限分别为0.03~0.6 ng/L(水)和0.006~0.134 μg/kg(蜂蜜)。在实际环境水样和蜂蜜样品中,加标回收率为72.1%~116.2%,重复使用10次后萃取性能仍保持稳定,体现出良好的实用性与可重复使用性。
抗生素、抗炎药、镇痛药及类固醇等药物被列为影响环境、食品及生物体的一类新兴污染物。人用与兽用药物经代谢后可能以原化合物或代谢物形式进入环境。此外,这些药物的过度使用、非法使用及不完全代谢可能导致其在环境和加工食品中残留,对消费者健康构成威胁。
NSAIDs是一类广泛用于治疗人类头痛、发热及炎症的抗炎镇痛药物。其结构中的羧基使其具有高水溶性,并可通过多种途径污染环境水体。同时,NSAIDs的过度使用也会导致其在动物源性食品中残留,严重影响人类健康。为了实现环境水样与食品样品中痕量NSAIDs的高效富集与检测,本课题组根据NSAIDs含有羧基及芳香苯环的结构特点,制备了两种新型富含氨基的MMONs复合物,即Fe3O4@MON-PEI600和MMON-PANI,用于MSPE环境水样与肉类样品中的NSAIDs[42,43]。Fe3O4@MON-PEI600与MMON-PANI结构中含有丰富的疏水作用、静电吸引、氢键及π-π作用位点,为高效萃取NSAIDs奠定了基础。此外,通过对其形貌和复合物浓度的调控可进一步对其富集性能进行调节。以MMON-PANI为例,其海胆状的形貌可提供更大的比表面积(202.9 m2/g)和与NSAIDs接触的面积,协同上述作用机理共同提高对NSAIDs的萃取效率。通过对比Fe3O4、Fe3O4-PANI、MMON和MMON-PANI的富集因子证明了MONs骨架和PANI是高效萃取NSAIDs的关键。同时,MMON-PANI在8次萃取-解吸循环后其回收率、吸附剂形貌和结构与新制备的几乎一致,表明其优异的可重复使用性和稳定性。所建立的富集和检测方法中,吸附剂用量和萃取时间分别仅需3 mg和6 min,显示出良好的应用前景。
FQs抗生素具有抗菌谱广、易吸收、成本低等优点,广泛应用于人类医学、畜牧业及水产养殖中细菌性疾病的预防与治疗。基于FQs结构的两性特征,Li等[24]设计并合成了首例两性离子型MMON-SO3H-NH2吸附剂(图4),并用于肉类样品中FQs的高效萃取。MMON-SO3H-NH2具有明确的核-壳结构,并可通过骨架预先设计的-SO3H与-NH2基团为FQs提供氢键、π-π及离子对相互作用位点。所建立的MMON-SO3H-NH2-MSPE-HPLC-UV方法检测鸡肉、牛肉及猪肉样品中的FQs,线性范围为0.15~1 000 μg/L、检出限低至0.05~4.5 μg/L、定量限为0.15~13 μg/L、富集因子为82.1~99.6。通过DFT计算证明了两性离子对相互作用位点在萃取两性FQs中的关键作用。该研究为FQs的富集与检测提供了可靠方法,并拓展了两性离子MMONs在MSPE两性目标物中的应用。
CEFs抗生素常用于治疗革兰氏阳性与阴性菌引起的疾病,其低副作用与快速起效的特点使其在人与动物疾病治疗中广泛应用。然而,CEFs的过度使用常导致其在动物源性食品中残留与累积。因此,本课题组[33]合成了一种新颖的双官能团MMON-COOH-2CONH,用于高效萃取奶粉样品中的3种CEFs。DFT计算并结合对比实验、红外吸收光谱和X-射线光电子能谱等结果表明,离子键、氢键、π-π及疏水相互作用促进了所有CEFs在MMON-COOH-2CONH上的富集。同时,MMON-COOH-2CONH在15次萃取-解吸循环后其回收率仍可保持在80%以上,证明其优异的可重复使用性和稳定性。与其他报道的方法相比,该方法具有更低的检出限(1~3 µg/kg)、更短的萃取时间(6 min)、更低的吸附剂用量(3 mg)、更少的有机溶剂消耗(0.4 mL)及更简单的样品前处理步骤,为复杂样品中CEFs的分析提供了新型高效磁性吸附剂。
作为近年来的新兴污染物,抗癫痫药物(AEDs),尤其是卡马西平,受到了广泛关注。研究表明,长期暴露于AEDs对水生生物及人类具有多种风险。Xu等[36]根据AEDs结构中富集氮元素的特性,以4-巯基苯硼酸为修饰剂,通过巯基-炔点击PSM策略合成了PBA修饰的Fe3O4@CD-MON-PBA。该吸附剂为AEDs提供了氢键、主客体作用及特异性B-N配位位点,实现了环境水样中痕量AEDs的高效富集与检测。PBA的引入不仅可增加B-N配位位点,还增强了Fe3O4@CD-MON-PBA的亲水性,最终提升了其对水中AEDs的萃取性能。该吸附剂具有优异的稳定性,例如,将Fe3O4@CD-MON-PBA浸泡在水、有机溶剂和不同pH溶液中7天仍可保持结构稳定,且经8次萃取-解吸循环后吸附剂对AEDs的回收率可稳定在82%以上。所发展的方法抗基质干扰能力较好,在复杂医院废水中的基质效应值介于87.4%~104.0%。作者还对比了Fe3O4@CD-MON-PBA对AEDs(92.3~98.0)和含有邻苯二酚结构的黄酮类物质(61.2~67.9)的富集因子,证明了Fe3O4@CD-MON-PBA不仅具有B-N配位作用,还具有典型的苯硼酸-邻苯二酚结合作用。系列实验证明了Fe3O4@CD-MON-PBA对AEDs的高选择性。本工作表明Fe3O4@CD-MON-PBA在复杂环境样品中富集痕量AEDs的良好前景,并揭示了巯基-炔点击反应在PSM合成功能化磁性CD-MONs用于样品预处理的潜力。
EDCs是干扰人体内分泌系统的外源性物质,对生殖、发育及代谢功能都能产生负面影响。EDCs广泛存在于环境、个人护理品、日用品及食品包装材料中,易被人体摄入并引发多种健康问题。因此,迫切需要监测环境、食品及生物体中的痕量EDCs。EDCs种类繁多,包括PGRs、雌激素、酚类化合物、PAHs等。鉴于EDCs结构的多样性,合理设计功能化MMONs对提升其选择性与灵敏度至关重要。
酚类化合物作为一类主要的EDCs,广泛用作食品包装中的增塑剂与阻燃剂。2020年,Du等[14]报道了氨基功能化MMONs(Fe3O4@MON-NH2)的制备及其用于检测环境水样、饮料瓶及果汁样品中的酚类物质。所研究的4种酚类物质通过氢键、π-π及疏水相互作用而被高效富集。所建立的方法具有较宽的线性范围(0.05~1 000 μg/L)、低的检出限(0.015~0.030 μg/L)、高的富集因子(172~197)和吸附量(105.6~124.1 mg/g)。此外,Xu等[31]成功合成了一种新型的MCD-MON用于环境水样及食品外卖盒中双酚类EDCs的高效萃取与灵敏检测。由于所选择碘代CD以及线性4,4′-二乙炔基联苯单体的平面诱导作用,所合成的MCD-MON为Fe3O4掺杂的片层状形貌。该特殊形貌可为双酚类EDCs提供丰富可及的疏水、主客体、氢键及π-π作用位点,有利于双酚类EDCs的萃取。同时,片层形貌的堆积密度可通过调节单体的浓度和Fe3O4用量进行调控。但是,该MCD-MON单体消耗量较大,不适合大量制备及后期使用。类似地,Ali等[29]报道了一种磁性核壳MMON用于水中氯酚的快速检测。合成的MMON具有静电吸引、丰富的π-π及疏水作用位点,可有效萃取目标氯酚。
PAHs是广泛存在的环境与膳食污染物,具有致突变与致癌风险,严重威胁人类健康。He等[16]报道了基于Fe3O4@PDA@NMON的MSPE方法,用于检测环境水样中的痕量硝基酚及OH-PAHs。Fe3O4@PDA@NMON表现出优异的热和溶剂稳定性、高比表面积及良好的超顺磁性。该吸附剂含有丰富的苯环和萘环、羟基及亚胺基团,为所研究的OH-PAHs与硝基酚提供了疏水、氢键及π-π作用位点。同时,Fe3O4和NMON之间的PDA涂层可为OH-PAHs与硝基酚提供更多的疏水、氢键及π-π作用位点,协同提升其对目标物的富集性能。所建立的方法在0.18~500 μg/L范围内线性良好,检出限为0.055~0.090 μg/L。最终,在多种废水样品中成功检测到质量浓度为0.29~0.80 μg/L的OH-PAHs与硝基酚。
PGRs具有类似内源激素的作用,广泛用于促进植物生殖生长及提高作物和果蔬产量。PGRs残留可引起人体内分泌紊乱,导致性早熟、生殖功能障碍及癌症等疾病。基于PGRs含羧基和芳环的结构特征,He等[15]设计并合成了磁性Co@NC-MON-2NH2复合物,用于蔬菜中PGRs的高效MSPE。Co@NC-MON-2NH2具有大比表面积、良好磁性、高稳定性,并通过氢键、π-π及疏水等多种作用机制对PGRs表现出强亲和力。所建立的用于测定蔬菜样品中PGRs的MSPE-HPLC-UV方法线性范围为0.03~500 μg/L,精密度为1.5%~7.7%,检出限为0.009~0.150 μg/L,揭示了Co@NC-MON-2NH2复合物作为新型MSPE吸附剂的潜力,并为功能化MMONs的制备提供了新思路。最近,Li等[46]以TEB与季铵盐单体1,1′-(2,5-二溴-1,4-亚苯基)双(N,N,N-三甲基甲铵)溴化物(DBB)通过直接原位生长法合成了一种新的季铵盐MMONs(MMON-DBB-2),并将其作为高效磁性吸附剂用于快速、灵敏、选择性MSPE蔬菜样品中的PGRs。该吸附剂除了具有MONs固有的π-π作用位点外,其引入的季铵盐基团还提供了额外的离子交换与静电相互作用位点,通过这些作用力之间的协同实现了PGRs的高效萃取。该工作展示了季铵盐型MMONs在MSPE领域良好的应用潜力,为设计和合成新型阳离子型MMONs提供了新途径。
众所周知,长期暴露于雌激素,即使浓度极低,也会严重干扰人体内分泌系统。此外,许多疾病与体内雌激素水平异常有关,包括儿童性早熟、乳腺癌及前列腺癌等。因此,准确监测复杂生物样品中雌激素浓度水平具有重要意义。Xu等[32]报道了通过溶剂与单体调控合成核-壳结构磁性CD-MON吸附剂(Fe3O4@CD-MON)的研究(图5),并结合LC-MS/MS分析和测定血液与尿液样品中的4种雌激素。所建立的方法具有良好线性范围(2.0~400 μg/L)、高富集因子(183~198)、低检出限(0.5~1.0 μg/L)与定量限(1.5~3.0 μg/L)、吸附剂用量少(3 mg)及良好的可重复使用性(至少8次)等特点。该工作证实了溶剂与单体调控合成Fe3O4@CD-MON的可行性,并揭示了其高效富集复杂生物样品中痕量雌激素的应用前景。
食品添加剂可增强食品风味与延长保质期。然而,食品添加剂使用不当或过量使用也会导致严重健康问题,包括头痛、恶心及内分泌紊乱等。因此,严格监管食品添加剂使用对确保食品安全至关重要。2023年,本课题组报道了室温合成新型的羟基与氨基双功能化MMON(MMON-B),用于食品中香兰素添加剂的检测[47]。MMON-B具有丰富的π-π、疏水及氢键作用位点,能高效快速富集食品样品中的香兰素,并表现出高回收率(86.4%~108.2%)与低检出限(0.10~0.15 μg/L)。该研究展示了室温合成双功能化MMONs的可行性。
极性芳香胺(AAs)是应用广泛的化工原料,具有潜在的致癌性和毒性风险,自1994年以来被国际癌症研究机构列为重要的人类可能致癌物(2A类)。食品包装是延长保质期、提升品质、保持新鲜度和营养价值的常用手段,但过程中也可能导致有毒化合物如AAs从包装材料迁移至食品中。鉴于茶饮料在日常生活中的巨大消费量及其对包装材料的广泛使用,建立灵敏、特异的检测方法测定茶饮料中的AAs对保障人类健康和食品安全至关重要。Zhong等[48]合成了一种磺酰胺功能化的MMONs(MMON-SO2NH2),通过预先设计的静电吸引、π-π作用、疏水作用及氢键等多种相互作用,成功实现了对茶饮料中AAs的高效萃取。该材料展现出较大的比表面积(304.4 m2/g)、快速的磁响应性(38.3 emu/g,<15 s)以及良好的稳定性和可重复使用性(>8次),是理想的AAs磁性吸附剂。
真菌毒素是霉菌在霉变食品中产生的代谢产物,会对人与动物造成严重危害,包括细胞毒性、内分泌干扰、致癌及致突变性等。因此,预防食品霉变及监测农产品霉菌污染意义重大。其中,黄曲霉毒素是霉变食品中最常见的真菌毒素,也是公共卫生领域的研究重点。为此,Li等[49]以Fe3O4为核、MOF/MON为壳层制备了一种新型核-壳磁性Fe3O4@UiO-66-NH2@MON复合物。该吸附剂可用于富集谷物中多种黄曲霉毒素,并具有良好的化学稳定性、高灵敏度(0.15~0.87 μg/L)及选择性。该方法为食品中痕量黄曲霉毒素的特异性测定提供了可靠手段,为监测食品与作物中黄曲霉毒素水平提供了有效途径。最近,Wang等[50]采用原位生长合成法制备了-NH2和-SO3H双功能化MMONs(Fe3O4@MON-NH2-SO3H)。在室温下,该吸附剂对黄曲霉毒素B1和B2的吸附量分别为69.5 mg/g和39.3 mg/g。此外,与Welchrom AOZ、Welchrom BRP和Cleanert ODS C18 3种商业萃取剂相比,所合成的Fe3O4@MON-NH2-SO3H对黄曲霉毒素展现出更优异的萃取性能,阐明了氢键、疏水作用、π-π相互作用以及分子尺寸筛分等多种相互作用模式是实现对药食同源样品中黄曲霉毒素高效、高选择性富集的基础。最终,所建立的方法成功用于20种药食同源样品中痕量黄曲霉毒素的检测。此后,Wang等[51]建立了以Fe3O4@MON-NH2-OH为MSPE吸附剂结合HPLC检测的方法,用于中药中痕量玉米赤霉烯酮(ZEN)的测定。所建立的方法线性范围为5~2 500 μg/L,检出限为1.4~35 μg/L,吸附量为215.0 mg/g,并成功应用于10种中药中ZEN的检测,回收率为80.7%~106.0%。
PFASs是一类烷基链上氢原子被氟原子取代的有机化合物,由于其良好的化学稳定性、强疏水性及防污性能,广泛应用于各类工业与消费品中。然而,PFASs可以在环境中持久存在,并可通过食物链对人类健康产生毒性效应。近期,Zhang课题组[37]以新型氟功能化MON-NH₂(Fe₃O₄@MON-NH₂@F7)作为MSPE吸附剂,通过吸附剂与PFASs之间的静电吸引、疏水、F-F、π-CF及氢键等相互作用,开发了一种快速、灵敏、准确测定水样、人血清及人卵泡液样品中的PFASs的方法。该方法线性范围宽(2~2 000 ng/L)、检出限低(0.54~1.47 ng/L),在复杂实际样品分析中表现较好(回收率81.7%~121.6%)。
本综述详细阐述了MMONs的合成方法和其作为磁性吸附剂在多种复杂样品中高效MSPE有机污染物的应用。相较于其他磁性吸附剂,MMONs凭借独特的结构特征、优异的化学与热稳定性、高吸附容量及较好的超顺磁性,逐渐成为一类可用于MSPE多种化合物的新兴磁性吸附剂。得益于其固有的共轭苯环结构、高比表面积、良好的可重复使用性以及易于修饰的特点,功能化MMONs通常可提供丰富的氢键、π-π堆积、疏水及静电相互作用位点,从而能够从食品、环境及生物样品等复杂基质中选择性地萃取从非极性到极性的各类痕量分析物,包括农药、PAHs、药物、EDCs、真菌毒素、PFASs和食品添加剂等。
然而,MMONs的合成、性能提升和机理研究仍存在以下问题亟待解决:(1)就功能化MMONs的合成而言,目前仍严重依赖昂贵且种类有限的功能单体,这大大阻碍了其广泛应用;PSM虽然能有效解决这一问题,但目前应用较多的仍为巯基-炔“点击”化学反应;MMONs复合物仅PEI和PANI两例,其种类及数量亟需扩充;(2)就MMONs的性能提升而言,目前MMONs的选择性还有待提升;(3)机理研究手段仍比较单一或简单。
因此,针对上述问题,未来应考虑在以下几个方面进行深入研究:(1)设计和拓展低成本的功能单体,丰富现有功能单体的种类和数量,例如廉价易得的天然产物、其他领域的商品化试剂等;发展其他有效的PSM合成功能化MMONs方法;引入其他功能性的复合物制备MMONs复合物;目前MMONs的合成仍需使用有毒有害试剂,亟须探索环境友好的制备方法合成功能化MMONs;(2)开发以目标物为导向的结构设计或功能化策略构建功能化MMONs,以提升其对目标物的选择性;(3)发展其他先进表征和机理探究手段如理论模拟、原位红外、固体紫外、拉曼光谱等,对MMONs的萃取机理进行深入研究,以期指导MMONs的结构设计或功能化。总之,本综述不仅可以深化研究人员对基于MMONs的MSPE方法用于富集和检测各类目标物的认识,也为MMONs的合成与应用提供了一定参考。
  • 国家自然科学基金(22174071).
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doi: 10.3724/SP.J.1123.2025.12010
  • 接收时间:2025-12-12
  • 首发时间:2026-10-29
  • 出版时间:2026-10-08
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  • 收稿日期:2025-12-12
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National Natural Science Foundation of China (No. 22174071).
国家自然科学基金(22174071).
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    1山东第一医科大学药学院(药物研究所), 山东 济南 250117

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https://castjournals.cast.org.cn/joweb/sepu/CN/10.3724/SP.J.1123.2025.12010
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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