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基于SNW-1磁性固相萃取牛奶中磺胺类药物

宁芊 陈钰 严志明

宁芊,陈钰,严志明. 基于SNW-1磁性固相萃取牛奶中磺胺类药物 [J]. 福建农业学报,2020,35(10):1154−1161 doi: 10.19303/j.issn.1008-0384.2020.10.014
引用本文: 宁芊,陈钰,严志明. 基于SNW-1磁性固相萃取牛奶中磺胺类药物 [J]. 福建农业学报,2020,35(10):1154−1161 doi: 10.19303/j.issn.1008-0384.2020.10.014
NING Q, CHEN Y, YAN Z M. SNW-1 Magnetic Solid Phase Extraction for HPLC Detection of Sulfonamides Residue in Milk [J]. Fujian Journal of Agricultural Sciences,2020,35(10):1154−1161 doi: 10.19303/j.issn.1008-0384.2020.10.014
Citation: NING Q, CHEN Y, YAN Z M. SNW-1 Magnetic Solid Phase Extraction for HPLC Detection of Sulfonamides Residue in Milk [J]. Fujian Journal of Agricultural Sciences,2020,35(10):1154−1161 doi: 10.19303/j.issn.1008-0384.2020.10.014

基于SNW-1磁性固相萃取牛奶中磺胺类药物

doi: 10.19303/j.issn.1008-0384.2020.10.014
基金项目: 国家自然科学基金青年科学基金项目(31801640)
详细信息
    作者简介:

    宁芊(1983−),女,硕士,讲师,研究方向:食品质量与安全控制(E-mail:53736131@qq.com

    通讯作者:

    严志明(1983−),男,博士,讲师,研究方向:食品安全分析与检测(45765545@qq.com

  • 中图分类号: TS 207.3

SNW-1 Magnetic Solid Phase Extraction for HPLC Detection of Sulfonamides Residue in Milk

  • 摘要:   目的  制备磁性共价有机骨架材料(Fe3O4@SNW-1)作为磁性固相萃取吸附剂,建立牛奶中磺胺类药物(SAs)的高效液相色谱(HPLC)测定方法。  方法  通过水热法合成Fe3O4@SNW-1,并通过研究吸附剂用量、吸附时间、洗脱剂、洗脱时间等影响因素,优化磁性固相萃取磺胺类药物的回收率,最后通过高效液相色谱法(HPLC)检验优化后方法的效果。  结果  优化后的MSPE条件:即用2.0 mL氨水-甲醇(5 95,v/v)作为洗脱溶剂,解吸时间设为60 s,吸附剂Fe3O4@SNW-1的用量为4.0 mg,吸附时间为120 s,pH值为6.0。经优化后,5种SAs的线性范围为10~100 ng·mL−1,相关系数在0.995以上,检出限为1.7~2.7 ng·mL−1。5种SAs(每种50 ng·mL−1)的5次重复提取的日间RSDs为2.8%~4.7%。5种SAs的回收率在72.0%~95.0%  结论  该方法方便快捷,选择性好,分离效果高,对牛奶中痕量磺胺类药物含量的检测效果良好。
  • 图  1  磁性固相萃取剂结构

    Figure  1.  Schematic diagram of MSPE

    图  2  磁性固相萃取流程

    Figure  2.  Flow diagram of MSPE

    图  3  Fe3O4及Fe3O4@SNW-1透射电镜表征结果

    注:a: Fe3O4; b: Fe3O4@SNW-1。

    Figure  3.  TEM images of Fe3O4 and Fe3O4@SNW-1

    Note:a: Fe3O4; b: Fe3O4@SNW-1.

    图  4  Fe3O4和Fe3O4@SNW-1的XRD衍射表征

    Figure  4.  XRD characterization on Fe3O4 and Fe3O4@SNW-1

    图  5  Fe3O4和Fe3O4@SNW-1的氮气吸附表征

    Figure  5.  Nitrogen adsorption characterization on Fe3O4 and Fe3O4@SNW-1

    图  6  吸附剂用量的影响

    Figure  6.  Effect of adsorbent usage on testing

    图  7  吸附时间的影响

    Figure  7.  Effect of adsorption time on testing

    图  8  不同pH的影响

    Figure  8.  Effect of pH on testing

    图  9  不同离子强度的影响

    Figure  9.  Effect of ionic strength on testing

    图  10  不同洗脱溶剂的影响

    注:1.v(氨水): v(甲醇)= 5:95, 2.v(乙酸): v(甲醇)=5:95, 3.v(氨水): v(乙腈)= 5:95, 4.v(乙酸): v(乙腈)=5:95,5.乙腈,6.甲醇。

    Figure  10.  Effect of eluent on testing

    Note: 1. ammonia -methanol(5:95, v/v); 2. acetic acid - methanol(5:95, v/v); 3. ammonia - acetonitrile(5:95, v/v); 4. acetic acid - acetonitrile(5:95, v/v); 5. acetonitrile; 6. methanol.

    图  11  洗脱剂体积的影响

    Figure  11.  Effect of eluent volume on testing

    图  12  不同解吸时间的影响

    Figure  12.  Effect of elution duration on testing

    图  13  不同处理样品色谱图

    注:A:空白牛奶样品的色谱图;B:加标牛奶样品的色谱图;C:采用MSPE处理的加标牛奶样品的色谱图。

    Figure  13.  Chromatograms of samples

    Note: A: Chromatogram of milk samples; B: Chromatogram of spiked milk samples after extraction; C: Chromatogram of spiked milk samples with MSPE.

    表  1  以磁性COF为吸附剂的MSPE/HPLC测定SAs的检出限及精密度

    Table  1.   Detecting limit and precision of MSPE/HPLC method using magnetic COF as adsorbent on SA determination

    分析物
    Analyte
    线性范围
    Linear range/(ng·mL−1
    线性方程
    Regression equation
    相关系数
    Correlation coefficient
    检出限
    Limit of detection/(ng·mL−1
    相对标准偏差
    RSD/%
    SDZ 10~100 y=643798x−416.89 0.999 0 1.7 3.4
    SMR 10~100 y=783 373x−543.79 0.998 1 1.7 2.8
    SMZ 10~100 y=697 128x−256.47 0.999 6 2.0 2.4
    SMM 10~100 y=754 506x−551 0.999 3 2.4 2.5
    SMX 10~100 y=654 838x− 2 976.6 0.994 8 2.7 2.8
    下载: 导出CSV

    表  2  牛奶样品中SAs的分析结果

    Table  2.   Analysis of SAs in milk samples

    分析物
    Analyte
    添加量
    Added/(ng·g−1
    牛奶 Milk
    测定值
    Found/(ng·g−1
    回收率
    Recovery/%
    相对标准偏差
    RSD/%
    SDZ 0 ND
    20 16.8 84 3.2
    50 38.5 77 2.8
    100 72 72 4.4
    SMR 0 ND
    20 18.6 93 6.1
    50 41 82 4.6
    100 79 79 5.3
    SMZ 0 nd
    20 19 95 2.3
    50 41.5 83 3.5
    100 81 81 5.8
    SMM 0 ND
    20 16.6 83 4.9
    50 40 80 3.1
    100 81 81 5.9
    SMX 0 ND
    20 17.6 88 5.7
    50 44 88 4.7
    100 86 86 3.4
    注:ND: 未检出。
    Note:ND means not detected.
    下载: 导出CSV

    表  3  所提方法与文献中其他方法的比较

    Table  3.   Comparison between MSPE/HPLC and other existing methods

    吸附剂
    Sorbent
    方法
    Method
    样品
    Sample
    吸附剂量
    Amount of
    Sorbent/mg
    样品容量
    Sample volume/
    mL
    萃取时间
    Extraction time/
    min
    洗脱剂体积
    Elution volume/
    mL
    检测限
    LODs/(ng·mL−1
    参考文献
    Reference
    Fe3O4-SiO2-phenylMSPE/HPLC牛奶 Milk10010537~14[25]
    Fe3O4-graphene oxideMSPE/HPLC水 Water5120150~100[26]
    HCP-Fe3O4MSPE/HPLC牛奶 Milk2025522.0~2.5[18]
    CoFe2O4-grapheneMSPE/HPLC牛奶 Milk15100200.51.16~1.59[27]
    Fe3O4@SNW-1MSPE/HPLC牛奶 Milk41022.01.7~2.7本研究 This work
    下载: 导出CSV
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  • 收稿日期:  2019-09-02
  • 修回日期:  2020-01-29
  • 刊出日期:  2020-10-28

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