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1 7 6 Vol. 7 No Journal of Food Safety and Quality Jun., * 李秀英, 陈树东, 王强, 叶嘉荣, 梁宇, 侯向昶, 郭新东 (, ) 摘要 : 目的 - (dispersive solid-phase extraction-gas chromatography, dspe-gc) 7 方法 15 min, 25 mg C mg PSA 10 mg MWCNT, DB-1701 结果 7 1.0~100 mg/l, ~0.9996; 2.6~5.0 mg/kg; mg/kg, %~107%, (n=6) 1.9%~5.3%; (n=5) 4.5%~9.1% 10, 1, 9.1 mg/kg 结论, 关键词 : ; ; ; Simultaneous determination of 7 kinds of alkylamines in food contact plastic package materials by gas chromatography coupled with dispersive solid-phase extraction LI Xiu-Ying, CHEN Shu-Dong, WANG Qiang, YE Jia-Rong, LIANG Yu, HOU Xiang-Chang, GUO Xing-Dong * (Guangzhou Quality Supervision and Testing Institute, Guangzhou , China) ABSTRACT: Objective To establish a new method for the simultaneous determination of 7 kinds of alkylamines in food contact plastic package materials by gas chromatography coupled with dispersive solid phase extraction (dspe-gc). Method The plastic sample was extracted with dichloromethane by ultrasonication for 15 min, and purified with solid phase extractant including 25 mg C 18, 25 mg PSA and 10 mg MWCNT. Then the extract was separated by column of DB-1701 and determined by gas chromatography. Meanwhile, the type of extraction solvent, clean-up sorbent and column were optimized. Result Seven kinds of alkylamines had a good linear relationship in the range of 1.0~100 mg/l with correlation coefficient of ~0.9996, the limit of detection was ranged from 2.6 mg/kg to 5.0 mg/kg. The mean recoveries spiked at 3 levels of 5.0, mg/kg were in the range of 81.9%~107%. The precision was 1.9%~5.3% (n=6), and the inter-precision was 4.5%~9.1% (n=5). Ten plastic packaging materials 基金项目 : (2015QK162) Fund: Supported by the Scientific and Technological Project of General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China (2015QK162) * 通讯作者 :,, gdone@21cn.com *Corresponding author: GUO Xin-Dong, Professor, Guangzhou Quality Supervision and Testing Institute, No.38, Baqier Road, Guangzhou , China. gdone@21cn.com

2 were tested for penicillamine, and only one was found positive and the concentration was 9.1 mg/kg. Conclusion The method is rapid and accurate, which can be used for determination of alkylamines compounds in food contact plastic packaging materials. KEY WORDS: alkylamines; dispersive solid phase extraction; food contact plastic package materials; gas chromatography 1 引言,,, [1,2], 3320 mg/kg [3, 4],, N- 2009,, 107 ( ) [5] N,N- 258 ( ) [6], 1, 6- PA, 2.4 mg/kg( 1, 6- ),,,, [7,8] [9,10] - [11,12] - [13-16] ;, 5- -1, 3, 3-4, , [17],, [18], (gas chromatography, GC) (penicillamine) (cyclo propylamine) N, N- -1, 3- (N, N'-dimethyl-1, 3-propanediamine) N, N- -1, 3- (N, N'-Diethyl-1,3-propanediamine) 1, 6- (1,6-hexanediamine) 1, 4- (1, 4-butanediamine) 5- -1, 3, 3- (isophorondiamine)7 ( 1) 2 材料与方法 2.1 仪器 试剂与材料 7890A (, 7683, Agilent ); MS2 Minshaker ( IKA ); 3K15 ( Sigma ); KQ-250DV ( ) 5- -1,3,3-1,4- N, N- 1,3- N,N- -1,3-1,6- Fig Structures of 7 kinds of alkylamines

3 6, : ,3,3- (isophorondiamine) 1,4- (1, 4-butanediamine) 1,6- (1, 6-hexanediamine)(penicillamine) N, N- 1, 3- (N, N'-Dimethyl-1, 3-propanediamine) N,N- -1,3- (N,N'-diethyl-1,3-propanediamine)(cyclo propylamine), CNW, 98%;, Merck ; (MWCNT, I.D. 3~5 nm, O.D. 8~15 nm, 50 nm, 95 %, ); (TLC ); C 18 N- (primary secondary amine, PSA) CNW 2.2 实验方法 标准溶液的配制 7 : 10.0 mg, 10 ml, 1000 mg/l 4 7 : 7, 100 mg/l, mg/l 样品前处理 3 mm 3 mm, : 1.0 g ( g) 10 ml, 6 ml,, 15 min, 10 ml, 1 ml 25 mg PSA 25 mg C mg MWCNT 2 ml, 1 min, r/min 2 min,, GC :, : 1.0 g ( g) 10 ml,,,, 气相色谱条件 : DB-1701(30 m 0.53 mm, 0.50 μm) ; :,, 1.0 ml/min; : 60, 2 min, 10 /min 150, 1 min, 15 /min 240, 10 min; : 200 ; : 1 μl, ( 10: 1); : 结果与讨论 3.1 色谱条件的优化 ,3,3-, DB-5 DB-1701 HP-INNOWAX 7 HP-INNOWAX N, N- 1,3- N, N- 1,3-, DP-1701 DB-5, 7,,, DB-1701 DB-5 ( 2),, DB Fig. 2 GC chromatogram of mixture standard solution of 7 kinds of alkylamines (1. ; 2. ; 3. 1,4- ; 4. N,N- -1,3- ; 5. N,N- -1,3- ; 6. 1,6- ; ,3,3- )

4 萃取溶剂的选择, 7, 7 3, (82.9%~95.8%),, (50.3%~78.16%), (acrylonitrile, ABS) (polystyrene, PS) (polypropylene, PP),,, 3.3 超声提取时间的优化 min 7 ( 4),, ; 15 min,, 15 min 3.4 净化条件的优化,, QuEChERS,, PSA MWCNT C 18 5 ( 5),,,, 40.0%~56.1%; C 18 PSA MWCNT 3 (90% ) PSA 2,, ; C 18 ; MWCNT,,,, PSA C 18 MWCNT, MWCNT PSA C 18 MWCNT, 0~20 mg,, 1.5 ml 10 mg MWCNT PSA mg, 85.5% 91.4% 93.8% 93.5% 92.1%, 25 mg C mg PSA 10 mg MWCNT, 95.8% 3.5 线性方程及检出限, Y X(mg/L), ~100 mg/l ( 1),, (S/N) (the instrument detection limit, ILOD), (10 ), 7 (method detection limit, MLOD) 1, MLOQ 2.6~5.0 mg/kg, Fig. 3 Effect of various solvents on the extraction recoveries of 7 alkylamines (1. ; 2. ; 3. 1,4- ; 4. N,N- -1,3- ; 5. N,N- -1,3- ; 6. 1,6- ; ,3,3- )

5 6, : mg/kg, 81.9%~107%, (RSD, n=6) 1.9%~5.3%;, (n=5) 4.5%~9.1%,, Fig. 4 Effect of ultrasonic time on the extraction recoveries of 7 alkylamines (1. ; 2. ; 3. 1,4- ; 4. N,N- -1,3- ; 5. N,N- -1,3- ; 6. 1,6- ; ,3,3- ) 3.6 回收率 精密度试验, 3, 6, ; (10.0 mg/kg) 5 d, 2, (n=3) Fig. 5 Effect of various sorbent on the clean-up recoveries of 7 alkylamines (n=3) (1. ; 2. ; 3. 1,4- ; 4. N,N- -1,3- ; 5. N,N- -1,3- ; 6. 1,6- ; ,3,3- ) 表 1 7 种烷基胺的线性方程 方法检出限和方法定量限 Table 1 Linear regression equations, MLOD of 7 kinds of alkylamines (mg/l) (mg/l) (mg/l) (mg/kg) ~100 Y=5711X ~100 Y=9717X ,4-1.00~100 Y=10051X N,N- -1,3-1.00~100 Y=6649X N,N- -1,3-1.00~100 Y=7228X ,6-1.00~100 Y=8416X ,3,3-1.00~100 Y=9006X 表 2 7 种烷基胺的加标回收率及精密度 Table 2 Recoveries and RSD of 7 kinds of alkylamines (%, n=6) (%, n=5) 5.0 mg/kg 10 mg/kg 50 mg/kg 10 mg/kg % RSD% % RSD % % RSD% % RSD% , N,N- -1, N,N- -1, , ,3,

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