色谱

色谱 ›› 2026, Vol. 44 ›› Issue (4): 422-431.DOI: 10.3724/SP.J.1123.2025.03012

• 研究论文 • 上一篇    下一篇

基于低共熔溶剂和改进针式滤头的液膜微萃取结合高效液相色谱法测定牛奶中磺胺与氟喹诺酮残留

徐锐洺1,2, 吴友谊1,2,*(), 顾智灏1,2, 魏唯1,2, 陆星宇1,2, 夏紫菡1   

  1. 1.苏州科技大学环境科学与工程学院，江苏 苏州 215009
    2.江苏省环境科学与工程重点实验室，江苏 苏州 215009
  • 收稿日期:2025-03-09 出版日期:2026-04-08 发布日期:2026-04-13
  • 通讯作者: * Tel：0512-68247000，E-mail：youyiwu@usts.edu.cn.
  • 基金资助:
    江苏省重点研发计划项目(BE2022733);江苏省研究生科研与实践创新计划(SJCX23_1713);江苏省研究生科研与实践创新计划(SJCX24_1906)

Deep eutectic solvent and improved needle filter-based liquid-membrane microextraction combined with high performance liquid chromatography for the determination of sulfonamide and fluoroquinolone residues in milk

XU Ruiming1,2, WU Youyi1,2,*(), GU Zhihao1,2, WEI Wei1,2, LU Xingyu1,2, XIA Zihan1   

  1. 1. School of Environmental Science and Engineering，Suzhou University of Science and Technology，Suzhou 215009，China
    2. Jiangsu Key Laboratory of Environmental Science and Engineering，Suzhou 215009，China
  • Received:2025-03-09 Online:2026-04-08 Published:2026-04-13
  • Supported by:
    Jiangsu Provincial Key Research and Development Project(BE2022733);Postgraduate Research & Practice Innovation Program of Jiangsu Province(SJCX23_1713);Postgraduate Research & Practice Innovation Program of Jiangsu Province(SJCX24_1906)

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摘要：

乳制品中抗生素残留威胁食品安全，影响人体健康。为准确测定牛奶中磺胺（SAs）和氟喹诺酮（FQs）抗生素残留水平，本研究建立了基于低共熔溶剂（DES）和改进针式滤头-液膜微萃取（DES&INF-LMME）结合高效液相色谱（HPLC）检测牛奶样品中这两类抗生素残留的分析方法。筛选出辛酸为氢键供体、百里酚为氢键受体，合成疏水性DES作为膜萃取的萃取剂和支撑液膜（SLM）。进而考察了DES种类及用量、百里酚和辛酸的物质的量之比、萃取膜种类、样品体积、盐种类及添加量、pH值、转速和萃取时间等因素对萃取效率的影响，得到最佳萃取条件：DES（百里酚-辛酸（2∶1，n/n））用量为100 μL，采用聚四氟乙烯（PTFE）膜滤头，样品溶液体积为30 mL（添加3 g硫酸铵，调节溶液pH为7），萃取转速400 r/min，萃取时间35 min。在优化条件下，所开发DES&INF-LMME-HPLC方法的线性范围为2.86~1 000 μg/L（r2>0.997 2），检出限为0.86~10.0 μg/L（S/N=3），定量限为2.86~33.3 μg/L（S/N=10）。富集倍数（EF）为32~84，回收率为99.4%~109.2%。在高、中、低加标水平下，日内、日间精密度分别≤4.9%和≤5.3%。该方法已成功应用于市售牛奶产品中4种抗生素的测定，在高、中、低3水平下4种抗生素的加标回收率为88.9%~113.4%。本方法准确、简便、灵敏，环境友好，可为乳制品中抗生素残留检测的新方法开发提供参考。

关键词: 低共熔溶剂, 针式滤头, 液膜微萃取, 抗生素残留, 牛奶样品

Abstract:

Antibiotic residues in dairy products pose serious threats to food safety and affect human health. To accurately determine the level of sulfonamide and fluoroquinolone residues in milk， a deep eutectic solvent and improved needle filter-based liquid membrane microextraction （DES&INF-LMME） method combined with high performance liquid chromatography （HPLC） was developed for their determination in this study. Octanoic acid （hydrogen bond donor） and thymol （hydrogen bond acceptor） were selected to synthesize hydrophobic deep eutectic solvent， which acted as supporting liquid membrane （SLM） and extractant in the LMME process. Further investigations were conducted to examine the effects of various factors on extraction efficiency， including type and volume of DES， molar ratio of thymol to octanoic acid， type of extraction membrane， sample volume， salt type and addition amount， pH value， stirring speed and extraction time. The optimal extraction conditions were determined as follows： DES∶thymol-octanoic acid=2∶1 （n/n）， 100 μL； filter membrane， polytetrafluoroethylene （PTFE）； sample volume and pH， 30 mL （addition of 3 g ammonium sulfate） and pH=7； stirring speed， 400 r/min； extraction time， 35 min. Under the optimized conditions， the proposed DES&INF-LMME-HPLC exhibited good linearity in the range of 2.86-1 000 μg/L （r2>0.997 2）， with limits of detection （LODs） （S/N=3） and limits of quantification （LOQs） （S/N=10） ranging from 0.86-10.0 μg/L and 2.86-33.3 μg/L， respectively. The obtained enrichment factors （EFs） ranged from 32 to 84 with recoveries of 99.4%-109.2%. The intra-day and inter-day precisions at three spiked levels （low： 30 μg/L； medium： 50 μg/L； high： 100 μg/L）， expressed as relative standard deviations （RSDs）， were no more than 4.9% and 5.3%， respectively （n=6）. This method has been successfully applied to the determination of four antibiotics in commercially available milk products. The spiked recoveries for the four antibiotics at high， medium and low levels ranged from 88.9% to 113.4%. The proposed method is accurate， simple， sensitive and eco-friendly， and could be a good reference to the development of new analytical method for antibiotic residues in dairy products.

Key words: deep eutectic solvent （DES）, improved needle filter （INF）, liquid-membrane microextraction （LMM）, antibiotic residues, milk samples

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