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

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

宁芊^1,,
陈钰²,
严志明^2, ,

1.
福建农林大学金山学院，福建　福州　350002
2.
福建农林大学食品科学学院，福建　福州　350002

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
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出版历程
- 收稿日期: 2019-09-02
- 修回日期: 2020-01-29
- 刊出日期: 2020-10-28

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

NING Qian^1
,,
CHEN Yu²,
YAN Zhiming^{2
, ,}

1.
Jinshan College, Fujian Agriculture and Forestry University, Fuzhou, Fujian　350002, China
2.
College of Food Science, Fujian Agriculture and Forestry University, Fuzhou, Fujian　350002, China

摘要

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。
- 共价有机骨架 /
- 样品前处理 /
- 磁性固相萃取 /
- 牛奶 /
- 磺胺类药物
Abstract: Objective Fe₃O₄@SNW-1 was prepared as an adsorbent in the magnetic solid phase extraction (MSPE) to pre-treat samples for HPLC determination on sulfonamides (SAs) in milk. Method A magnetic covalent organic framework (COF) material, Fe₃O₄@SNW-1, was hydrothermally synthesized to serve as the adsorbent in MSPE for the sample pretreatment. Parameters for the pretreatment, including adsorbent usage, adsorption duration, eluent selection, and elution time that affected the extract recovery, were optimized. HPLC was used to evaluate and determine the validity of the methodology. Result The optimized MSPE applying 2.0 mL ammonia-methanol (5 ∶ 95, V/V) as elution solvent, 60s for desorption, 4.0 mg of Fe₃O₄@SNW-1 as adsorbent, 120 s for adsorption at pH 6.0 to achieve linearities in the ranges between 10 ng·mL⁻¹ and 100 ng·mL⁻¹ on detecting 5 different SAs with correlation coefficients greater than 0.995. The HPLC detection limit on the SAs was 1.7-2.7 ng·mL⁻¹. The daytime RSDs of 5 extraction replicates on the SAs (50 ng·mL⁻¹ each) were 2.8–4.7%. The recovery rates on the SAs varied from 72.0% to 95.0%. Conclusion The proposed HPLC method with the MSPE sample pretreatment was convenient, rapid, specific, and effective for the determination of trace amounts of SA residues in milk.
- Covalent organic frameworks /
- sample pretreatment /
- magnetic solid phase extraction /
- milk /
- sulfonamides

HTML全文

图 1 磁性固相萃取剂结构

Figure 1. Schematic diagram of MSPE

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图 2 磁性固相萃取流程

Figure 2. Flow diagram of MSPE

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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.

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图 4 Fe₃O₄和Fe₃O₄@SNW-1的XRD衍射表征

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

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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

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图 6 吸附剂用量的影响

Figure 6. Effect of adsorbent usage on testing

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图 7 吸附时间的影响

Figure 7. Effect of adsorption time on testing

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图 8 不同pH的影响

Figure 8. Effect of pH on testing

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图 9 不同离子强度的影响

Figure 9. Effect of ionic strength on testing

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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.

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图 11 洗脱剂体积的影响

Figure 11. Effect of eluent volume on testing

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图 12 不同解吸时间的影响

Figure 12. Effect of elution duration on testing

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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.

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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

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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
分析物 Analyte	添加量 Added/（ng·g⁻¹）	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.

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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-phenyl	MSPE/HPLC	牛奶 Milk	100	10	5	3	7～14	[25]
Fe₃O₄-graphene oxide	MSPE/HPLC	水 Water	5	1	20	1	50～100	[26]
HCP-Fe₃O₄	MSPE/HPLC	牛奶 Milk	20	25	5	2	2.0～2.5	[18]
CoFe₂O₄-graphene	MSPE/HPLC	牛奶 Milk	15	100	20	0.5	1.16～1.59	[27]
Fe₃O₄@SNW-1	MSPE/HPLC	牛奶 Milk	4	10	2	2.0	1.7～2.7	本研究 This work

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