Determination of sulfonamides by ultra-high performance liquid chromatography with microextraction
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摘要: 探究了三相中空纤维膜微萃取-超高效液相色谱（HF-LPME-UHPLC）方法，用于测定鸡肉中6种磺胺类药物残留.设计了三相中空纤维膜微萃取系统，优化HF-LPME最佳萃取条件：正辛醇作为萃取剂，接收相中NaOH的浓度为0.2 mol/L，给出相样品溶液中盐酸浓度为1.0 mmol/L，Na2SO4浓度为375 g/L，萃取温度为30℃，搅拌速度为300 r/min，萃取时间为4 h.6种磺胺类药物经萃取后进行色谱分析，在6 min内达到了基线分离，线性关系良好，R2均大于0.9989，富集倍数为188~950倍，检出限为0.03~0.1 ng/mL（S/N=3）.加标浓度为50μg/kg的鸡肉组织样品的加标回收率为85.2%~95.6%，相对标准偏差为3.13%~4.33%（n=5）.表明本方法灵敏度高、重复性好，可用于鸡肉中磺胺类抗生素的检测.Abstract: In this study, the development of an analytical method for the determination of chicken meat based on three-phase hollow fiber membrane microextraction ultra-high performance liquid chromatography (HF-LPME-UHPLC) was explored. A three-phase hollow fiber membrane microextraction system was developed to optimize the extraction conditions of HF-LPME:the extractant was n-octanol, the concentration of NaOH in the receiving phase was 200 mmol/L, the concentration of hydrochloric acid in the sample solution was 1.0 mmol/L, the concentration of Na2SO4 was 375 g/L, the extraction temperature was 30°, the stirring rate was 300 r/min, and the extraction time was 4 hours. Chicken meat samples were extracted and analyzed by UHPLC. Chromatographic analysis showed that the six sulfonamides reached baseline separation within six minutes. The linearity of the six sulfonamides in the mass range was good with a correlation coefficient of R2 > 0.998 9, the enrichment factors ranged from 188 to 950 times, and the detection limit was 0.03~0.1 ng/mL (S/N=3). The recoveries of sulfonamides flagged in chicken were 85.2%~95.6% with relative standard deviations of 3.13%~4.33% (n=5) at a concentration of 50 μg/kg. The studied method is highly sensitive and reproducible, and can be used for the detection of sulfonamides in chicken.
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图 2 6种磺胺的高效液相色谱图
Fig. 2 Chromatogram of standard solution of six sulfonamides by UHPLC
图 3 NaOH浓度对富集倍数的影响
Fig. 3 Effect of the concentration of NaOH on EFs of six sulfonamide compounds
图 4 盐酸浓度对富集倍数的影响
Fig. 4 Effect of the concentration of hydrochloric acid on EFs of six sulfonamide compounds
图 5 浓度对富集倍数的影响
Fig. 5 Effect of the concentration of Na2SO4 on EFs of six sulfonamide compounds
图 6 温度对富集倍数的影响
Fig. 6 Effect of the extraction temperature on EFs of six sulfonamide compounds
图 7 萃取时间对富集倍数的影响
Fig. 7 Effect of the extraction time EFs of six sulfonamide compounds
图 8 搅拌速度对富集倍数的影响
Fig. 8 Effect of the stirring rate on EFs of six sulfonamide compounds
表 1 6种磺胺类抗生素的线性关系、相关系数和检出限
Tab. 1 Linear equations, correlation coefficients, and detection limits of six sulfonamide antibiotics
化合物 线性范围/(ng· mL-1) 线性方程a 相关系数R2 检出限/(ng· mL-1) SMX (0.12~5.04)× 104 y=2.11× 108x+4.91× 104 0.999~8 0.05 SDM (0.42~1.01)× 105 y=7.03× 108x +5.93× 105 0.998~9 0.10 SM1 (0.22~5.09)× 104 y=2.19× 108x+1.02× 105 0.999~2 0.10 SMZ (0.13~5.05)× 104 y=2.19× 108x+7.13× 104 0.999~5 0.04 SAs (0.11~5.05)× 104 y=3.31× 108x+9.02× 105 0.999~3 0.03 SD (0.12~5.07)× 104 y=8.09× 107x+2.51× 105 0.999~4 0.05 注: x为磺胺浓度(μ g/mL), y为磺胺的峰面积(AU); S/N=3, 进样量10 μL 
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表 2 6种抗生素的加标回收率及标准偏差
Tab. 2 RSD and recovery of six sulfonamides
化合物 回收率/% RSD/%(n=5) SMX 91.5 3.81 SDM 88.4 4.33 SM1 95.2 3.13 SMZ 88.0 3.81 SAs 86.3 3.64 SD 95.6 3.24
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