UPLC/Orbitrap HRMS法同时测定皮革及其制品中26种限用酚类化合物

Simultaneous Determination of 26 Restricted Phenolic Compounds in Leather and Leather Products by UPLC/Orbitrap HRMS

建立了超高效液相色谱/静电场轨道阱高分辨质谱(UPLC/Orbitrap HRMS)同时测定皮革及其制品中含氯酚类、烷基酚类和双酚A共3大类26种酚类化合物残留量的方法。该方法以甲醇为萃取溶剂,超声萃取皮革及其制品中残留的酚类化合物,萃取产物经固相萃取柱净化后进行超高效液相色谱/静电场轨道阱高分辨质谱(UPLC/Orbitrap HRMS)分析,从而建立了一个同时测定皮革及其制品中26种酚类化合物的分析方法。色谱分离在Accucore aQ色谱柱(150 mm×2.1 mm,2.6μm)上完成,流动相为甲醇/2 mmol/L乙酸铵水溶液,洗脱方式为梯度洗脱。质谱分析采用电喷雾负离子(ESI-)模式,质谱扫描范围为m/z 50~m/z 750。利用保留时间和准分子离子精确质量数进行定性,利用提取离子色谱峰面积进行外标法定量。在3个不同加标浓度水平下,该方法的加标平均回收率为76.85%~95.32%,相对标准偏差为3.05%~12.46%。辛基酚(OP)、庚基酚(HpP)、戊基酚(PeP)、苯酚(Phenol)的定量下限分别为2、10、20、100μg/kg,其余22种酚类化合物的定量下限为0.05~1.00μg/kg。该方法定性可靠,定量准确,灵敏度高,可实现对皮革及其制品中26种酚类化合物的同时测定。采用该方法对市售皮革及其制品进行检测,结果在部分样品中检出不同浓度水平的酚类化合物。

An effective method was established for the simultaneous determination of 26 phenolic compounds in leather and leather products using ultra-high performance liquid chromatography/Orbitrap high resolution mass spectrometry(UPLC/Orbitrap HRMS)technique.Phenolic compounds in leather and leather products were ultrasonically extracted using methanol as the extraction solvents.The extract was then purified by solid-phase extraction(SPE)column,followed by the analysis of UPLC/Orbitrap HRMS.The chromatographic separation was carried out on an Accucore aQ column(150 mm×2.1 mm,2.6μm)with a gradient elution of methanol/2mmol/L ammoniumacetate solution.The mass spectrometry analysis was performed by Orbitrap high resolution mass spectrometry in ESI-mode.Full-scan experiment was carried out in the range from m/z 50 to m/z 750.The qualitative analysis was carried out by the retention time and the accurate mass of quasi-molecular ion.The quantitative analysis was carried out by the peak area in extracted chromatogram and the concentration of each target compounds was calibrated by the external standard method.The blank samples were spiked at three levels and the average spiked recoveries changed from 76.85%to 95.32%while the relative standard deviation(RSD)changed from 3.05%to 12.46%.The limit of quantification(LOQ)was 2、10、20、100μg/kg for octylphenol(OP),heptylphenol(HpP),pentylphenol(PeP)and phenol,respectively.The limits of quantification(LOQs)were in the range from 0.05?g/kg to 1.00μg/kg for the other 22 phenolic compounds.The proposed method was qualitatively reliable,accurate and sensitive,applicable for the simultaneous determination of 26 phenolic compounds in leather and leather products.The proposed method was applied to the detection of commercially available leather and leather products,and phenolic compounds at different concentration levels were detected in some samples.