血液透析导管中残留单体二苯基甲烷二异氰酸酯的检测
|
摘要
背景:目前,含聚氨酯医疗器械的质量控制文件和技术标准中均未明确残留单体二苯基甲烷二异氰酸酯(diphenylmethane diisocyanate,MDI)的控制指标及检测方法,考虑到MDI对人体具有致癌的潜在风险,为控制该类产品的安全有效性,应及早建立质量标准。目的:建立测量血液透析导管中残留单体MDI的测试方法,分析该产品的MDI溶出量对人体是否存在风险。方法:取血液透析导管样品用乙酸乙酯加热回流,采用气相色谱法分析MDI含量。色谱条件为:DB-5 MS色谱柱(30 m×0.25 mm),起始温度60℃,保持5 min,然后以15℃/min升至280℃,保持6 min;进样口温度280℃;检测器:FID,温度280℃;载气:氦气,99.999%。结果与结论:MDI在4.970-99.40 mg/L(r=0.999 64)范围线性关系良好;平均加标回收率为100.9%,相对标准偏差(RSD)=3.2%(n=6)。3批样品的MDI残留量低于可耐受接触量。该方法灵敏、快速、准确、专属性强,可为血液透析导管的质量标准研究提供依据。
BACKGROUND: In the current quality control file or technical standards of the hemodialysis catheter, the indicators of the component contents and detection methods of the residual diphenylmethane diisocyanate(MDI) monomer are undefined. To ensure the safety and effectiveness of these products, we should try to establish and improve the quality standards. OBJECTIVE: To establish a method for determination of the residual MDI monomer in a hemodialysis catheter by gas chromatography(GC), and to analyze the bio-security of the MDI. METHODS: Samples collected in the hemodialysis catheter were heated to reflux with ethyl acetate and theresidual MDI content was analyzed by the GC. The GC separation was performed on a DB-5 MS column(30 m×0.25 mm), the temperature of which rose by program. The initial temperature was 60 ℃, maintained for 5 minutes, rose to 280 ℃ with a rate of 15 ℃/min, and maintained for 6 minutes. The temperature of the Injector and FID detector was both 280 ℃. Carrier gas was 99.999% nitrogen. RESULTS AND CONCLUSION: The linearity was achieved in the range of 4.970-99.40 mg/L(r=0.999 64) for MDI. The mean recovery rate was 100.9% with the relative standard deviation of 3.2%(n=6). The residue of MDI monomer in the three batches of samples was lower than the tolerable exposure. Therefore, it is a sensitive, rapid, accurate, specific method that can be used for the quality control of the residual MDI monomer in the hemodialysis catheter.
BACKGROUND: In the current quality control file or technical standards of the hemodialysis catheter, the indicators of the component contents and detection methods of the residual diphenylmethane diisocyanate(MDI) monomer are undefined. To ensure the safety and effectiveness of these products, we should try to establish and improve the quality standards. OBJECTIVE: To establish a method for determination of the residual MDI monomer in a hemodialysis catheter by gas chromatography(GC), and to analyze the bio-security of the MDI. METHODS: Samples collected in the hemodialysis catheter were heated to reflux with ethyl acetate and theresidual MDI content was analyzed by the GC. The GC separation was performed on a DB-5 MS column(30 m×0.25 mm), the temperature of which rose by program. The initial temperature was 60 ℃, maintained for 5 minutes, rose to 280 ℃ with a rate of 15 ℃/min, and maintained for 6 minutes. The temperature of the Injector and FID detector was both 280 ℃. Carrier gas was 99.999% nitrogen. RESULTS AND CONCLUSION: The linearity was achieved in the range of 4.970-99.40 mg/L(r=0.999 64) for MDI. The mean recovery rate was 100.9% with the relative standard deviation of 3.2%(n=6). The residue of MDI monomer in the three batches of samples was lower than the tolerable exposure. Therefore, it is a sensitive, rapid, accurate, specific method that can be used for the quality control of the residual MDI monomer in the hemodialysis catheter.
引文
[1]中蓝晨光化工研究设计院有限公司.2014~2015年世界塑料工业进展[J].塑料工业,2016,44(3):1-46.
[2]张丽.我国聚氨酯产业现状分析及展望(待续)[J].化学工业,2015,33(1):15-18.
[3]张丽.我国聚氨酯产业现状分析及展望(续完)[J].化学工业,2015,33(Z1):12-22.
[4]4,4'-Methylenediphenyl diisocyanate and polymeric4,4'-methylenediphenyl diisocyanate.IARC Monogr Eval Carcinog Risks Hum.1999;71 Pt 3:1049-1058.
[5]Concise International Chemical Assessment Document 27,DIPHENYLMETHANE DIISOCYANATE(MDI),WHO,2000.
[6]Schwab SJ.Hemodialysis vascular access:the Achilles'heel remains.Kidney Int.2007;72(6):665-666.
[7]Cornelis T,Usvyat LA,Tordoir JH,et al.Vascular access vulnerability in intensive hemodialysis:a significant Achilles'heel.Blood Purif.2014;37(3):222-228.
[8]US Renal Data System:USRDS 2002 Annual Data Report.Bethesda,National Institutes of Health,National Institute of Diabetes and Digestive and Kidney Diseases,2002,chapt 4.
[9]2003 annual report:ESRD clinical performance measures project.Am J Kidney Dis.2004;44(2 Suppl 1):A5-6,S1-92.
[10]李绍雄,刘益军.聚氨酯树脂及其应用[M].北京:化学工业出版社,2004:305.
[11]李汾.医用聚氨酯弹性体[J].科技情报开发与经济,2001,11(4):95-96.
[12]潘才元.功能高分子[M].北京:科学出版社,2006.
[13]钟金汤.偶氮染料及其代谢产物的化学结构与毒性关系的回顾与前瞻[J].环境与职业医学,2004,21(1):58-62.
[14]徐德珍,贺一训.偶氮染料中微量芳香胺类的分析方法现状[J].印染,1996(3):26-30.
[15]杨晓芬,李军湘.N-氯代丁二酰亚胺8-羟基喹哪啶分光光度法测定水中苯胺类化合物的方法研究[J].内蒙古石油化工,2002,27(1):25-26.
[16]马立斌,宋春娟.甲萘酚代替萘乙二胺测定水中苯胺类化合物[J].河北工业科技,2000,17(4):21-22.
[17]杨晓芬,赵美萍,李元宗,等.水中苯胺类化合物的分光光度法测定[J].分析化学,2002,30(5):540-543.
[18]Longo M,Cavallaro A.Determination of aromatic amines at trace level by derivatization with heptafluorobutyric an hydride and gas Chromatography-electron-capture negative-ion chemical ionization analysis spectrometry.J Chromatogr A.1996;753:91-100.
[19]Kataoka H.Derivatization reactions for the determination of amines by gas chromatography and their applications in environmental analysis.J Chromatogr A.1996;733(1-2):19-34.
[20]Schmidt TC,Less M,Haas R,et al.Gas chromatographic determination of aromatic amines in water samples after solid-phase extraction and derivatization with iodine.I.Derivatization.J Chromatogr A.1998;810(1-2):161-172.
[21]海勇,田树盛.致癌芳香胺的检测[J].印染助剂,2005,22(9):42-45.
[22]Huang M,Tai C,Zhou Q,et al.Preparation of polyaniline coating on a stainless-steel wire using electroplating and its application to me determination of six aromatic amines using headspace splid-phase micrextraction.J Chromatogr A.2004;1048(2):257-262.
[23]Kataoka H.Derivatization reactions for the determination of amines by gas chromatography and their applications in environmental analysis.J Chromatogr A.1996;733(1-2):19-34.
[24]Brede C,Skjevrak I,Herikstad H.Determination of primary aromatic amines in water food simulant using solid-phase analytical derivatization followed by gas chromatography coupled with mass spectrometry.J Chromatogr A.2003;983(1-2):35-42.
[25]Singh V,Gupta M,Jain A,et al.Determination of aromatic primary amines at microg l(-1)level in environmental waters by gas chromatography-mass spectrometry involving N-allyl-n'-arylthiourea formation and their on-line pyrolysis to aryl isothiocyanates.J Chromatogr A.2003;1010(2):243-253.
[26]Chang WY,Sung YH,Huang SD.Analysis of carcinogenic aromatic amines in water samples by solid-phase microextraction coupled with high-performance liquid chromatography.Analytica Chimica Acta.2003;495(1):109-122.
[27]陈为都,王小妹,黄仲立.IPDI及MDI型聚氨酯预聚体中游离二异氰酸酯含量测定[J].聚氨酯工业,2009,24(2):43-46.
[28]姚洁,胡晓佳,王庆印,等.4,4'-二苯甲烷二异氰酸酯的高效液相色谱分析[J].化学通报,2008(6):457-460.
[29]栾杨,李翎,王晓云,等.高效液相色谱测定车间空气中4,4'-二苯甲烷二异氰酸酯[J].中国公共卫生,1999,15(10):937-938.
[30]姚洁,王公应.4,4'-二苯甲烷二异氰酸酯的HPLC分析[J].天然气化工,2005,30(5):68-70.
[31]张敏,雷兴红.涂料中游离甲苯二异氰酸酯的气相色谱测定法[J].环境与健康杂志,2003,20(6):364-365.
[32]郭巧珍,杜振霞.UPLC-MS/MS测定二苯甲烷二异氰酸酯[J].质谱学报,2011,32(2):112-116.
[33]Zhu Y,Wang M,Du H,et al.Organic analysis by ion chromatography.1.Determination of aromatic amines and aromatic diisocyanates by cation-exchange chromatography with amperometric detection.J Chromatogr A.2002;956(1-2):215-220.
[34]黄甫.苯胺及其衍生物的毛细管电泳行为研究[J].理化检验化学分册,2003,39(12):696-699.
[2]张丽.我国聚氨酯产业现状分析及展望(待续)[J].化学工业,2015,33(1):15-18.
[3]张丽.我国聚氨酯产业现状分析及展望(续完)[J].化学工业,2015,33(Z1):12-22.
[4]4,4'-Methylenediphenyl diisocyanate and polymeric4,4'-methylenediphenyl diisocyanate.IARC Monogr Eval Carcinog Risks Hum.1999;71 Pt 3:1049-1058.
[5]Concise International Chemical Assessment Document 27,DIPHENYLMETHANE DIISOCYANATE(MDI),WHO,2000.
[6]Schwab SJ.Hemodialysis vascular access:the Achilles'heel remains.Kidney Int.2007;72(6):665-666.
[7]Cornelis T,Usvyat LA,Tordoir JH,et al.Vascular access vulnerability in intensive hemodialysis:a significant Achilles'heel.Blood Purif.2014;37(3):222-228.
[8]US Renal Data System:USRDS 2002 Annual Data Report.Bethesda,National Institutes of Health,National Institute of Diabetes and Digestive and Kidney Diseases,2002,chapt 4.
[9]2003 annual report:ESRD clinical performance measures project.Am J Kidney Dis.2004;44(2 Suppl 1):A5-6,S1-92.
[10]李绍雄,刘益军.聚氨酯树脂及其应用[M].北京:化学工业出版社,2004:305.
[11]李汾.医用聚氨酯弹性体[J].科技情报开发与经济,2001,11(4):95-96.
[12]潘才元.功能高分子[M].北京:科学出版社,2006.
[13]钟金汤.偶氮染料及其代谢产物的化学结构与毒性关系的回顾与前瞻[J].环境与职业医学,2004,21(1):58-62.
[14]徐德珍,贺一训.偶氮染料中微量芳香胺类的分析方法现状[J].印染,1996(3):26-30.
[15]杨晓芬,李军湘.N-氯代丁二酰亚胺8-羟基喹哪啶分光光度法测定水中苯胺类化合物的方法研究[J].内蒙古石油化工,2002,27(1):25-26.
[16]马立斌,宋春娟.甲萘酚代替萘乙二胺测定水中苯胺类化合物[J].河北工业科技,2000,17(4):21-22.
[17]杨晓芬,赵美萍,李元宗,等.水中苯胺类化合物的分光光度法测定[J].分析化学,2002,30(5):540-543.
[18]Longo M,Cavallaro A.Determination of aromatic amines at trace level by derivatization with heptafluorobutyric an hydride and gas Chromatography-electron-capture negative-ion chemical ionization analysis spectrometry.J Chromatogr A.1996;753:91-100.
[19]Kataoka H.Derivatization reactions for the determination of amines by gas chromatography and their applications in environmental analysis.J Chromatogr A.1996;733(1-2):19-34.
[20]Schmidt TC,Less M,Haas R,et al.Gas chromatographic determination of aromatic amines in water samples after solid-phase extraction and derivatization with iodine.I.Derivatization.J Chromatogr A.1998;810(1-2):161-172.
[21]海勇,田树盛.致癌芳香胺的检测[J].印染助剂,2005,22(9):42-45.
[22]Huang M,Tai C,Zhou Q,et al.Preparation of polyaniline coating on a stainless-steel wire using electroplating and its application to me determination of six aromatic amines using headspace splid-phase micrextraction.J Chromatogr A.2004;1048(2):257-262.
[23]Kataoka H.Derivatization reactions for the determination of amines by gas chromatography and their applications in environmental analysis.J Chromatogr A.1996;733(1-2):19-34.
[24]Brede C,Skjevrak I,Herikstad H.Determination of primary aromatic amines in water food simulant using solid-phase analytical derivatization followed by gas chromatography coupled with mass spectrometry.J Chromatogr A.2003;983(1-2):35-42.
[25]Singh V,Gupta M,Jain A,et al.Determination of aromatic primary amines at microg l(-1)level in environmental waters by gas chromatography-mass spectrometry involving N-allyl-n'-arylthiourea formation and their on-line pyrolysis to aryl isothiocyanates.J Chromatogr A.2003;1010(2):243-253.
[26]Chang WY,Sung YH,Huang SD.Analysis of carcinogenic aromatic amines in water samples by solid-phase microextraction coupled with high-performance liquid chromatography.Analytica Chimica Acta.2003;495(1):109-122.
[27]陈为都,王小妹,黄仲立.IPDI及MDI型聚氨酯预聚体中游离二异氰酸酯含量测定[J].聚氨酯工业,2009,24(2):43-46.
[28]姚洁,胡晓佳,王庆印,等.4,4'-二苯甲烷二异氰酸酯的高效液相色谱分析[J].化学通报,2008(6):457-460.
[29]栾杨,李翎,王晓云,等.高效液相色谱测定车间空气中4,4'-二苯甲烷二异氰酸酯[J].中国公共卫生,1999,15(10):937-938.
[30]姚洁,王公应.4,4'-二苯甲烷二异氰酸酯的HPLC分析[J].天然气化工,2005,30(5):68-70.
[31]张敏,雷兴红.涂料中游离甲苯二异氰酸酯的气相色谱测定法[J].环境与健康杂志,2003,20(6):364-365.
[32]郭巧珍,杜振霞.UPLC-MS/MS测定二苯甲烷二异氰酸酯[J].质谱学报,2011,32(2):112-116.
[33]Zhu Y,Wang M,Du H,et al.Organic analysis by ion chromatography.1.Determination of aromatic amines and aromatic diisocyanates by cation-exchange chromatography with amperometric detection.J Chromatogr A.2002;956(1-2):215-220.
[34]黄甫.苯胺及其衍生物的毛细管电泳行为研究[J].理化检验化学分册,2003,39(12):696-699.