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

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

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，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
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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

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

1.
Institute of Agricultural Quality Standards and Testing Technology Research, Fujian Academy of Agricultural Sciences/Fujian Key Laboratory of Agro-products Qualitiy & 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。
- 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 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.
- surface-enhanced Raman spectroscopy /
- enrofloxacin /
- ciprofloxacin /
- rapid detection

HTML全文

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

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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 nanoparticles 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. Trends of SERS signals of enrofloxacin with different reaction times（785 cm⁻¹）

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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

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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 with different particle sizes

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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

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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 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 ENR和CIP方法学评价结果

Table 2. Results of methodological evaluation of enrofloxacin

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" means undetected, below the detection limit of the method; "—" indicates no spiked recovery and RSD of undetected material.

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