漂浮固化分散液液微萃取-UHPLC-MS/MS法测定水产品中丁香酚的残留量

建立了漂浮固化分散液液微萃取（DLLME-SFO）前处理技术，结合超高效液相色谱-串联质谱（UHPLC-MS/MS）法测定水产品中丁香酚的残留量。通过考察萃取剂种类、萃取剂体积、分散剂种类、分散剂体积、氯化钠质量分数、萃取时间、离心温度对萃取效率的影响，确定了最佳萃取条件，即以30 μL 1-十一醇为萃取剂，800 μL 乙醇为分散剂，氯化钠质量分数为6%，于-3 ℃下以10000 r/min离心5 min，将液体部分移除，待固体融化后取20 μL 供UHPLC-MS/MS分析。结果表明，在5~500 μg/kg范围内，丁香酚的线性关系良好，相关系数为0.999 6，回收率在88.9%~103.4%之间，方法检出限和定量限分别为1.47 μg/kg和4.91 μg/kg，日内相对标准偏差(RSD)均低于7.5%（n=6），日间相对标准偏差(RSD)均低于9.8%（n=3）。该方法操作简单，溶剂用量少，快速、安全、重现性好，适用于水产品中丁香酚残留的分析。

Determination of Eugenol Residue in Aquatic Using Dispersive Liquid-Liquid Microextraction Based on the Solidification of a Floating Organic Droplet Followed by UHPLC-MS/MS

A novel dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) followed by ultra performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) was developed for the determination of eugenol residue in aquatic. The influence of extraction parameters including types of extraction solvent, volume of extraction solvent, vortex extraction time, sodium chloride mass fraction, chromatographic condition and mass spectrometry condition were investigated. The optimal liquid-liquid microextraction experiment conditions were as follows: 30 μL 1-undecanol as extraction solvent, 800 μL of methanol as disersive solvent, sodium chloride mass fraction 6%, vortex oscillation extrantion time 3 min, centrifugal time was 5 min with 10 000 r/min at three degrees below zero centigrade, dislodge water phase, after thawed it was analyzed by UHPLC-MS/MS. The analytical column was DIKMA Endeavorsil C18（30 mm×2.1 mm×1.8 μm）, and the mobile phase was composed of methanol-water solution (80∶20,V/V). The flow rate was 0.30 mL/min and run time was 2.0 min. A tandem mass spectrometer coupled with negative electro-spray ionization (ESI) source was used for detection. The quantitative detection was performed on UHPLC-MS/MS by multiple reaction monitoring (MRM) mode under negative electro spray ionization (ESI^-). It was shown that good linearity is obtained at the concentrations of 5.0-500.0 μg/kg with the correaltion coefficients higher than 0.999 6 for eugenol. The recovery is 88.9%-103.4%. The limits of detection (LOD) and limit of quantification (LOQ) for eugenol are 1.47 μg/kg and 4.91 μg/kg, respectively. The intra-day relative standard deviations are lower than 7.5%（n=6）, and the inter-day relative standard deviations are lower than 9.8%（n=3）. MRL of eugenol in aquatic product was not demanded in China. Therefore, analytical of eugenol content in different aquatic products is of considerable importance and requires the development of precise methods for its determination imperatively. The method is efficient, solvent saving, reliable and sensitive, and can be suitable for the determination of eugenol residue in aquatic.