Objective: To establish a gas chromatography method that could determine the residual hexamethyl cyclotrisiloxane(D3)、octamethyl cyclotetrasiloxane(D4)、decamethyl cyclopentasiloxane(D5)、dodecamethyl cyclohexasiloxane(D6) with potentially toxic in the medical rubber stopper and their migration in cephalosporins for injection. Methods: The DB-WAX capillary column(30 m×0.320 mm×0.25 μm)was used. The carrier gas was nitrogen and the volume of injection was 1 μL. The column flow rate was 1.5 mL·min-1 and the split ratio was 10∶1. Column temperature was first kept at 35 ℃ for 5 minutes, then raised to 180 ℃ with the rate of 10 ℃·min-1, then raised to 240 ℃ with the rate of 50 ℃·min-1 and maintained for 5 minutes. The temperature of the gasification chamber was 250 ℃. The detector was FID and the temperature was 250 ℃. Results: The four kinds of dimethyl cyclosiloxane had a good linear relationship(r≥0.999 7) in the range of 1.0-25.0 μg·mL-1. The limit of detection was 0.51, 0.50, 0.52, and 0.52 μg·mL-1, respectively. The average recovery was 93.8%, 95.7%, 95.6%, and 95.2%, respectively. The highest content of D3, D4 and D5 in bromobutyl rubber stopper was 15.74, 21.42, and 11.36 μg·g-1, respectively. The migration of D5 was 23.97 μg·g-1. Conclusion: The method is accurate with high sensitivity and good repeatability, which can be used for the assay of dimethyl cyclosiloxane and their migration in medicinal rubber stopper.
[1] 幸松民, 王一璐.有机硅合成工艺及产品应用[M].北京:化学工业出版社, 2000:9
XING SM, WANG YL. The Synthesis Process and Product Application of Organic Silicon[M].Beijing: Chemical Industry Press, 2000:9
[2] 许嘉祥, 陈奕伊, 陈萌萌, 等.硅油中微量二甲基硅氧烷环体的定量分析研究[J].杭州师范大学学报(自然科学版), 2018, 17(5):462
XU JX, CHEN YY, CHEN MM, et al. Study on the quantitative analysis of trace cyclicdimethylsiloxanes in silicone oil[J].J Hangzhou Normal Univ(Nat Sci Ed), 2018, 17(5):462
[3] SIDDIQUI WH, STUMP DG, PLOTZKE KP, et al. A two-generation reproductive toxicity study of octamethylcyclotetrasiloxane(D4) in rats exposed by whole-body vapor inhalation[J].Reprod Toxicol, 2007, 23(2):202
[4] VELICOGNA J, RITCHIE E, PRINCZ J, et al. Ecotoxicity of siloxane D5 in soil[J].Chemosphere, 2012, 87(1):77
[5] KIERKEGAARD A, VAN EGMOND R, MCLACHLAN MS. Cyclic volatile methylsiloxane bioaccumulation in flounder and ragworm in the humber estuary[J].Environ Sci Technol, 2011, 45(14):5936
[6] HONG WJ, JIA H, LIU C, et al. Distribution, source, fate and bioaccumulation of methyl siloxanes in marine environment[J].Environ Pollut, 2014, 191:175
[7] 张喜荣, 王文娟, 戚冬雷, 等.P&T-GC-MS法对食品接触硅胶奶嘴中VMSs的模拟迁移研究[J].包装工程, 2018, 39(15):21
ZHANG XR, WANG WJ, QI DL, et al. Simulated migration of VMSs in food-contact silicone teats by method of P&T-GC-MS[J].Pack Eng, 2018, 39(15):21
[8] OECD.The 2004 OECD list of high production volume chemicals[EB/OL]. (2013-05-23)[2021-08-17]. http://www.oecd.org/dataoecd/55/38/33883530.pdf
[9] 刘丹, 李委璐, 方丽, 等.气相色谱法测定二甲基环体硅氧烷[J].天津科技, 2021, 48(7):45
LIU D, LI WL, FANG L, et al. Determination of dimethyl cyclosiloxane by gas chromatography[J].Tianjin Sci Technol, 2021, 48(7):45
[10] 韩晶, 许勇, 潘晨, 等.洗护发化妆品中二甲基硅氧烷环体的测定[J].香料香精化妆品, 2021(2):68
HAN J, XU Y, PAN C, et al. Determination of dimethylsiloxane cyclic mixture in hair care cosmetics[J].Flavour Frag Cosmet, 2021(2):68
[11] 冯锁民, 冯家星, 周柄全, 等.红外分光光度法测定西甲硅油中聚二甲基硅氧烷的含量[J].中国食品添加剂, 2018(4):201
FENG SM, FENG JX, ZHOU BQ, et al. Study on the determination of simethicone by infrared spectrophotometry[J].China Food Add, 2018(4):201
[12] 林舒忆, 贾彦博, 陈美春, 等.空气/氩气双通气-原子吸收石墨炉法测定食用油中的二甲基硅氧烷[J].食品安全质量检测学报, 2020, 11(24):9226
LIN SY, JIA YB, CHEN MC, et al. Determination of the content of polydimethylsiloxane by graphite furnace atomic absorption spectrome[J].J Food Saf Qual, 2020, 11(24):9226
[13] HELLING R, KUTSCHBACH K, SIMAT TJ. Migration behaviour of silicone moulds in contact with differentfoodstuffs[J].Food Addit Contam, 2010, 27(3): 396
[14] 刘宜奇, 胡长鹰, 商贵芹, 等.食品接触用硅橡胶中3种环硅氧烷的测定及迁移规律[J].食品工业科技, 2020, 41(11):245
LIU YQ, HU CY, SHANG GQ, et al. Determination and migration of three kinds of cyclosiloxanes in food contact silicone rubber[J].Sci Technol Food Ind, 2020, 41(11):245
[15] 胡星宇, 熊马剑, 朱碧君.FTIR-ATR 法测定药用卤化丁基橡胶塞表面二甲基硅油残留量和在葡萄糖氯化钠注射液中的迁移量[J].药物分析杂志, 2019, 39(4):693
U XY, XIONG MJ, ZHU BJ.Determination of residual polydimethylsiloxane on the surface of medicinal halogenated butyl rubber[J].Chin J Pharm Anal, 2019, 39(4):693
[16] 于岩, 章若红, 钟毅, 等.用气相色谱-质谱法测定纺织柔软剂中的环硅氧烷[J].纺织学报, 2020, 41(8):69
YU Y, ZHANG RH, ZHONG Y, et al. Determination of cyclicsilicates in textile softeners by gas chromatography-mass spectrometry[J].J Text Res, 2020, 41(8):69
[17] 姚羽, 王文艳, 郭景文, 等.注射用氨苄西林钠中二甲硅油迁移量对澄清度的影响[J].药物分析杂志, 2013, 33(3):508
YAO Y, WANG WY, GUO JW, et al. Effect of migration of polydimethylsiloxane on clarity in ampicillin sodium for injection[J].Chin J Pharm Anal, 2013, 33(3):508
[18] 崇小萌, 董欣, 姚尚辰, 等.头孢唑林钠与胶塞相容性关系的探讨[J].中国抗生素杂志, 2019, 44(8):942
CHONG XM, DONG X, YAO SC, et al. Research on the compatibility between cefazolin sodium and rubber closures[J].Chin J Antibiot, 2019, 44(8):942
[19] 付蒙, 周姝, 袁怡, 等.卤化丁基胶塞对注射用西咪替丁与注射用多索茶碱澄清度的影响研究[J].药物分析杂志, 2020, 40(8):1459
FU M, ZHOU S, YUAN Y, et al. Effect of halogenated butyl rubber stoppers on the clarity in cimetidine for injection and doxofylline for injection[J].Chin J Pharm Anal, 2020, 40(8):1459