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

doi:10.19303/j.issn.1008-0384.2024.03.014

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

doi: 10.19303/j.issn.1008-0384.2024.03.014

1.
福建省农业科学院农业质量标准与检测技术研究所/福建省农产品质量安全重点实验室，福建　福州　350003
2.
厦门市普识纳米科技有限公司，福建　厦门　361021
3.
厦门市质量技术评审服务中心，福建　厦门　361021

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，E-mail：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，E-mail：870993292@qq.com

中图分类号: TS254.7
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- 被引次数: 0
出版历程
- 收稿日期: 2023-06-06
- 修回日期: 2023-12-07
- 网络出版日期: 2024-03-28
- 刊出日期: 2024-03-28

SERS Detection of Enrofloxacin and Ciprofloxacin Residues in Seafood

1.
Institute of Agricultural Quality Standards and Testing Technology Research, Fujian Academy of Agricultural Sciences/Fujian Key Laboratory of Agro-products Quality & Safety, Fuzhou, Fujian　350003, China
2.
Xiamen PERSer Nanotechnology Co., Ltd., Xiamen, Fujian　361021, China
3.
Xiamen Assessment Service Center of Quality and Technology, Xiamen, Fujian　361021, China

摘要

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 ENR和CIP的拉曼光谱特征峰为532、552 、651、737、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。
- 表面增强拉曼光谱 /
- 恩诺沙星 /
- 环丙沙星 /
- 快速检测
Abstract: Objective A rapid method for detecting residues of enrofloxacin (ENR) and ciprofloxacin (CIP) in seafood by surface-enhanced Raman spectroscopy (SERS) was developed. Method On spiked seafood samples, (50±5) nm silver nanoparticles were used as the enhancement reagent and 200 g·L⁻¹ NaCl solution as the extraction solution for the SERS assay. Detection results were read within 3 min and mathematical correlation between peak measurement and drug concentration examined. Based on the linearity and limit of detection, optimal assay conditions were determined. Result The assay showed several peaks on ENR and CIP standards. The C-N bending vibration caused the peak at 532 cm⁻¹, the out-of-plane bending vibration at 552 cm⁻¹, the C-N, C-C-F out-of-plane and C-C=O in-plane bending vibrations at 651 cm⁻¹, 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 at 737 cm⁻¹, and the C-H, C-N out-of-plane bending vibration at 785 cm⁻¹. By quantifying the characteristic peak at 737 cm⁻¹, a linear relationship with an R²＞0.96 was found between the Raman intensity and drug concentration in the range of 10–200 ng·mL⁻¹. The assay had a recovery rate of 78.4%~106.7%, RSD of 2.1%~6.7%, and a detection limit of 10 μg·kg⁻¹. Conclusion The newly developed rapid SERS assay for detecting ENR and CIP residues in seafood was deemed accurate, stable, and applicable for field screening and testing.
- Surface-enhanced Raman spectroscopy /
- enrofloxacin /
- ciprofloxacin /
- rapid detection

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图 1 增强试剂纳米金溶胶（A）和纳米银溶胶（B）电镜图

Figure 1. Electron microscopic images of gold (A) and silver (B) nanoparticles

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图 2 纳米金溶胶和纳米银溶胶的SERS谱图

Figure 2. SERS spectra of gold and silver nanoparticles

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图 3 不同反应时间的ENR的SERS信号变化趋势

Figure 3. SERS signals of ENR under various reaction times

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图 4 不同粒径的银纳米溶胶电镜图

Figure 4. Electron microscopic images of silver nanoparticles of various sizes

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图 5 不同粒径纳米银溶胶的SERS谱图

Figure 5. SERS spectra of silver nanoparticles of various sizes

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图 6 不同萃取溶剂的提取效果对比

a~e分别为NaOH溶液、石油醚溶液、二氯甲烷溶液、NaCl溶液和乙腈标准溶液。

Figure 6. Extractions by different solvents

a–e are NaOH solution, petroleum ether, dichloromethane, NaCl solution, acetonitrile standard solution, respectively.

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表 1 ENR和CIP不同提取液中的线性关系

Table 1. Linear relationships on different ENR and CIP extracts

样本 Sample	ENR		CIP
样本 Sample	R²	回归方程 Regression equation	R²	回归方程 Regression equation
草鱼 Ctenopharyngodon idella	0.964 6	y=193.74x+170.08	0.988 3	y=186.51x+182.51
南美白对虾 Litopenaeus Vannamei	0.972 4	y=187.25x+200.45	0.976 4	y=188.51x+212.43
中华绒螯蟹 Eriocheir Sinensis	0.981 5	y=215.69x+121.55	0.971 2	y=209.23x+126.98

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表 2 样品中ENR和CIP的加标回收率(n=5)

Table 2. Recovery rates of ENR and CIP in samples(n=5)

样本 Sample	ENR				CIP
样本 Sample	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: Undetected due to assay detection limit; —: lack of spiked recovery and RSD of undetected material.

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