在线凝胶渗透色谱-气相色谱-串联质谱非衍生化法测定食品中氯丙醇

Derivatization-free Method for Chloropropanols Determination in Food by Online Gel Permeation Chromatography-Gas ChromatographyTriple Quadrupole Mass Spectrometry

建立了食品中氯丙醇类化合物的非衍生化在线凝胶渗透色谱-气相色谱-串联质谱（Online GPC-GCMS/MS）测定方法,目标化合物包括3-氯-1,2-丙二醇（3-MCPD）、2-氯-1,3-丙二醇（2-MCPD）、1,3-二氯-2-丙醇（1,3-DCP）和2,3-二氯-1-丙醇（2,3-DCP）。样品中加入氘代同位素内标后,采用ExtrelutTMNT硅藻土进行固相支持液液萃取净化,用正己烷淋洗去除非极性杂质,以乙酸乙酯萃取目标物,萃取液经浓缩后直接采用Online GPC-GC-MS/MS测定。4种氯丙醇在0.005~1.000 mg/L范围内呈良好线性,相关系数均大于0.999,4种氯丙醇的检出限在0.002~0.005 mg/kg之间,定量限在0.005~0.01 mg/kg之间。以空白酱油样品为代表性基质的3个水平（0.02,0.1和0.5 mg/kg）的加标回收率和相对标准偏差（RSD,n=6）分别为94.8%~106.3%（2.2%~10.3%）,91.8%~108.8%（2.1%~10.6%）和83.1%~109.4%（1.3%~9.4%）。采用本方法分别对酱油、水解植物蛋白液（粉）、料酒、鸡精、面包和糕点样品进行检测,均得到了满意的测定结果。

A derivatization-free method for chloropropanols determination in food using online gel permeation chromatography-gas chromatography-triple quadrupole mass spectrometry （Online GPC-GC-MS/MS） with free of derivatization was established. The target compounds were 3-monochloropropane-1,2-diol （3-MCPD）, 2-monochloro-propane-1,3-diol （2-MCPD）, 1,3-dichloropropan-2-ol （1,3-DCP） and 2,3-dichloropropan-l-ol （2,3-DCP）. Samples were spiked with isotope internal standards, and extracted by matrix solid-supported liquid-liquid extraction on the ExtrelutTM NT absorbent. Hexane was added to wash away the apolar matrix interferences and then ethyl acetate was used to extract the target compounds. The concentrated extracts were directly injected into Online GPC-GC-MS/MS. The good linear relationships for the four types of analytes were obtained in the concentration range of 0. 005-1. 000 mg/L with correlation coefficients not less than 0. 999. The limits of detection and quantitation for chloropropanols in the food samples were in the ranges of 0. 002- 0. 005 mg/kg, and 0. 005-0.01 mg/kg respectively. The recoveries and the relative standard deviations （RSD, n = 6 ） for the spiked blank samples at the levels of 0.02, 0. 1, 0.5 mg/kg were in the ranges of 94.8% -106.3% （2.2%-10.3%）, 91.8% -108.8% （2.1%-10.6%） and 83.1% -109.4% （1.3%- 9.4% ）, respectively. The established method was applied to the samples of soy sauce, hydrolyzed vegetables protein solution and powder, cooking wine, chicken powder, bread and cake, and satisfactory results were acquired.