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表面增强拉曼光谱法快速检测水产品中恩诺沙星和环丙沙星残留

刘文静 潘葳 林惠真 陈宏炬 严绍德

刘文静,潘葳,林惠真,等. 表面增强拉曼光谱法快速检测水产品中恩诺沙星和环丙沙星残留 [J]. 福建农业学报,2024,39(X):1−8
引用本文: 刘文静,潘葳,林惠真,等. 表面增强拉曼光谱法快速检测水产品中恩诺沙星和环丙沙星残留 [J]. 福建农业学报,2024,39(X):1−8
LIU W - J, PAN W, LIN H - Z, et al. Determination of enrofloxacin and ciprofloxacin residues in aquatic products by Surface-enhanced Raman Spectroscopy [J]. Fujian Journal of Agricultural Sciences,2024,39(X):1−8
Citation: LIU W - J, PAN W, LIN H - Z, et al. Determination of enrofloxacin and ciprofloxacin residues in aquatic products by Surface-enhanced Raman Spectroscopy [J]. Fujian Journal of Agricultural Sciences,2024,39(X):1−8

表面增强拉曼光谱法快速检测水产品中恩诺沙星和环丙沙星残留

基金项目: 福建省科技计划公益类专项(2021R1022008);福建省农业高质量发展超越“5511”协同创新工程项目(XTCXGC2021020) ;福建省农业科学院创新团队建设项目(CXTD2021011-1)
详细信息
    作者简介:

    刘文静( 1982− ),女,硕士,助理研究员,主要从事农产品质量安全研究,411935637@qq.com

    通讯作者:

    潘葳(1970 — ),女,研究员,主要从事农产品质量安全研究,870993292@qq.com

  • 中图分类号: TS254.7

Determination of enrofloxacin and ciprofloxacin residues in aquatic products by Surface-enhanced Raman Spectroscopy

  • 摘要:   目的  建立基于表面增强拉曼光谱(Surface-enhanced Raman scattering,SERS)检测水产品中恩诺沙星(enrofloxacin,ENR)和环丙沙星(ciprofloxacin,CIP)残留的方法。  方法  以水产品为研究对象,采用粒径50±5 nm的银纳米溶胶作为SERS增强试剂,200 g·L−1 NaCl溶液作为萃取试剂,3 min内判读结果,并建立了峰强度与浓度的线性回归方程,考察线性关系和检出限,对该方法进行评价。  结果  结果表明,ENR和CIP的拉曼光谱特征峰为532 cm−1、552 cm−1、651 cm−1、737 cm−1和785 cm−1,其中532 cm−1归属于C-N的弯曲振动;552 cm−1归属于C-N面外弯曲振动;651 cm−1归属于C-N、C-C-F面外弯曲振动和C-C=O面内弯曲振动;737 cm−1归属于苯环上C-H的伸缩振动、C-C=O的面外弯曲振动、C-C-N弯曲振动;785 cm−1归属于C-H、C-N的面外弯曲振动。通过对ENR和CIP的特征峰(737 cm−1)进行定量分析发现拉曼特征峰强度与溶液浓度在10 ~200 ng·mL−1内有良好的线性关系,R2>0.96,加标回收率为78.4%~106.7%,RSD值为2.1%~6.7%,方法检出限为10 μg·kg−1  结论  该方法准确、快速、稳定,可实现ENR和CIP在水产品中的现场快速筛查检测。
  • 图  1  增强试剂纳米金溶胶电镜图和纳米银溶胶电镜图

    Figure  1.  Electron microscopy of gold nanoparticles and silver nanoparticles

    图  2  纳米金溶胶和纳米银溶胶的SERS谱图

    Figure  2.  SERS spectra of gold nanoparticles and silver nanoparticles

    图  3  不同反应时间的ENR的SERS信号变化趋势

    Figure  3.  Trends of SERS signals of enrofloxacin with different reaction times(785 cm−1

    图  4  不同粒径的银纳米溶胶电镜图

    Figure  4.  Electron microscopy of silver nanoparticles with different particle sizes

    图  5  不同粒径纳米银溶胶的SERS谱图

    Figure  5.  SERS spectra of silver nanoparticles with different particle sizes

    图  6  不同萃取溶剂的提取效果对比图

    a-e分别为NaOH溶液,石油醚溶液,二氯甲烷溶液,NaCL溶液,乙腈标准溶液

    Figure  6.  Comparison of different extraction solvents

    a-e are NaOH solution, petroleum ether ,dichloromethane , NaCL solution, acetonitrile standard solution

    表  1  ENR和CIP不同提取液中的线性关系

    Table  1.   Linear relationship for ENR and CIP in different extracts

    样本
    sample
    ENRCIP
    R2回归方程
    regression equation
    R2回归方程
    regression equation
    草鱼
    Ctenopharyngodon idella
    0.964 6y=193.74x+170. 080.988 3y=186.51x+182. 51
    南美白对虾
    Litopenaeus Vannamei
    0.972 4y=187.25x+200.450.976 4y=188.51x+212. 43
    中华绒螯蟹
    Eriocheir Sinensis
    0.981 5y=215.69x+121.550.971 2y=209.23x+126.98
    下载: 导出CSV

    表  2  ENR和CIP方法学评价结果

    Table  2.   Results of methodological evaluation of enrofloxacin

    样本
    Sample
    ENR CIP
    加标
    Add/(μg·kg−1
    结果
    Results/(μg·kg−1
    回收率
    recovery/%
    RSD
    (n=5)/%
    加标
    Add/(μg·kg−1
    结果
    Results/(μg·kg−1
    回收率
    recovery/%
    RSD
    (n=5)/%
    草鱼
    Ctenopharyngodon idella
    0 ND 0 ND
    10 9.71 97.1 3.5 10 9.32 93.2 3.2
    20 17.23 86.2 2.9 20 17.22 86.1 5.8
    50 46.54 93.1 4.9 50 45.69 91.4 6.4
    南美白对虾
    Litopenaeus Vannamei
    0 ND 0 ND
    10 8.42 84.2 6.7 10 9.65 96.5 2.4
    20 16.52 82.6 5.1 20 21.34 106.7 3.9
    50 48.35 96.7 3.2 50 44.25 88.5 5.7
    中华绒螯蟹
    Eriocheir Sinensis
    0 ND 0 ND
    10 10.12 101.2 5.8 10 9.95 99.5 6.5
    20 15.67 78.4 4.3 20 16.34 81.7 3.4
    50 47.33 94.7 2.1 50 45.35 90.7 4.9
    "ND"表示未检出,低于该方法的检出限;“—”表示未检出物质对应的无加标回收率和RSD值。
    "ND" means undetected, below the detection limit of the method; "—" indicates no spiked recovery and RSD of undetected material.
    下载: 导出CSV
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  • 收稿日期:  2023-06-06
  • 修回日期:  2023-12-07
  • 网络出版日期:  2024-03-28

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