Determination of enrofloxacin and ciprofloxacin residues in aquatic products by Surface-enhanced Raman Spectroscopy
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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。 Abstract: :Objective A rapid method for detection of Enrofloxacin (ENR)and ciprofloxacin (CIP) residues in vegetables and fruits by Surface-enhanced Raman spectroscopy (SERS) was established. Method The best detection conditions were obtained by screening of enhancement reagent, optimizing extraction solvents and reaction time using fruit and vegetable products as the research objects.The silver nanoparticles with a particle size of 50±5 nm was used as the SERS enhancement reagent, 200 g·L−1 NaCl solution was used as the extraction solution, and the results were interpreted within 3 min. The linear regression equation of peak intensity and concentration was established, and the linear relationship and detection limit were established to evaluate the method. Result The results indicate that, the Raman spectrograms peaks of ENR and CIP are 532 cm−1、552 cm−1、651 cm−1、737 cm−1and 785 cm−1, of which 532 cm−1 is caused by C-N bending vibration, and 552 cm−1 is the out-of-plane bending vibration, 651 cm−1 is attributed to C-N, C-C-F out-of-plane bending vibration and C-C=O in-plane bending vibration .737 cm−1 is attributed to the stretching vibration of C-H on the benzene ring, C-C=O out-of-plane bending vibration, C-C-N bending vibration and C-H, C-N stretching vibration, and 785 cm−1 is attributed to C-H, C-N out-of-plane bending vibration. By quantifying the characteristic peak(737 cm−1), the Raman intensity and the concentration have a good linear relationship within 10 ng·mL−1~200 ng·mL−1, and R2 > 0.96, the recovery rate was 78.4%~106.7%, the RSD was 2.1%~6.7%, and the method detection limit was 10 μg·kg−1. Conclusion The method is accurate, rapid, stable, and can achieve ENR and CIP in aquatic products in the field for rapid screening and detection. -
Key words:
- surface-enhanced Raman spectroscopy /
- enrofloxacin /
- ciprofloxacin /
- rapid detection
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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
sampleENR CIP R2 回归方程
regression equationR2 回归方程
regression equation草鱼
Ctenopharyngodon idella0.964 6 y=193.74x+170. 08 0.988 3 y=186.51x+182. 51 南美白对虾
Litopenaeus Vannamei0.972 4 y=187.25x+200.45 0.976 4 y=188.51x+212. 43 中华绒螯蟹
Eriocheir Sinensis0.981 5 y=215.69x+121.55 0.971 2 y=209.23x+126.98 表 2 ENR和CIP方法学评价结果
Table 2. Results of methodological evaluation of enrofloxacin
样本
SampleENR 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 idella0 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 Vannamei0 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 Sinensis0 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. -
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