药物及育发产品中己烯雌酚和双烯雌酚的卫生检测新方法研究
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摘要
己烯雌酚和双烯雌酚是结构相近的人工合成的非甾体雌酚类激素,临床上用于补充体内雌激素不足,治疗乳腺癌、前列腺癌、闭经和绝经期综合症等,并能够促使女性器官及副性征正常发育,促使子宫内膜增生,增强子宫收缩,提高子宫催产素的敏感性;小剂量刺激垂体前叶促性激素及催乳素的分泌,大剂量则起到抑制作用。双烯雌酚是己烯雌酚的体内代谢产物。在畜牧业中,己烯雌酚和双烯雌酚主要用于牛奶产量、促进蛋白质合成,具有增加蛋白质沉积和减少脂肪沉积的作用。长期使用己烯雌酚和双烯雌酚或食用含有己烯雌酚和双烯雌酚的奶制品或肉制品会导致妇女更年期紊乱、生育能力下降、女性性早熟、男性女性化,并能导致女性产生乳腺癌、子宫癌等。因此建立方便、快捷的己烯雌酚和双烯雌酚检测方法具有重要意义。
在碱性介质中,Ag(Ⅲ)配合物氧化鲁米诺产生稳定的化学发光信号,某些物质能显著增强或抑制鲁米诺-Ag(Ⅲ)体系的化学发光,并且发光强度与物质浓度在一定范围内呈良好的线性关系。本试验将Ag(Ⅲ)-鲁米诺化学发光新体系与流动注射技术相结合,建立了检测己烯雌酚的新方法,并将此方法应用于己烯雌酚片剂的含量测定。毛细管电泳将电泳技术与现代微柱分离技术相结合,以高压直流电场为驱动力,在毛细管中按各组分的淌度和分配行为的不同进行高效、快速的分离。毛细管电泳的分离通道为中空的毛细管,对样品的预处理要求较低,本研究旨在建立毛细管电泳法测定育发产品中己烯雌酚和双烯雌酚。
一、流动注射-Ag(Ⅲ)-鲁米诺化学发光新体系测定己烯雌酚片剂中己烯雌酚含量
目的:建立流动注射-Ag(Ⅲ)-鲁米诺化学发光新体系测定己烯雌酚片剂中己烯雌酚含量的新方法。
方法:在碱性条件下,鲁米诺被Ag(Ⅲ)氧化产生稳定的化学发光信号,己烯雌酚能显著抑制Ag(Ⅲ)-鲁米诺体系的化学发光作用,且发光强度与样品的浓度在一定范围内呈良好的线性关系。通过对鲁米诺溶液浓度、碱度和Ag(Ⅲ)溶液浓度、碱度等一系列发光条件进行优化选取,在最佳发光条件下绘制己烯雌酚的标准曲线,并对样品进行含量测定。
结果:流动注射-化学发光法测定己烯雌酚的最低检出限为3.0×10~(-7) mol/L。线性范围为5.0×10~(-7)-5.0×10~(-5) mol/L ,回归方程为△I=5.84×10~8C+548,线性相关系数r=0.9989。对1.0×10~(-5) mol/L的己烯雌酚连续进行平行测定7次,RSD为3.4%,加标回收率在88.6%-100.0%之间,RSD为3.7%。
结论:流动注射化学发光法测定己烯雌酚片剂中己烯雌酚含量,方法简便快捷、准确可靠,可用于己烯雌酚片剂生产过程己烯雌酚的质量控制。
二、毛细管电泳法测定育发产品中的己烯雌酚和双烯雌酚
目的:建立毛细管电泳-紫外检测法测定育发产品己烯雌酚和双烯雌酚含量的新方法。
方法:采用未涂层弹性熔融石英毛细管(75μm i.d.×55 cm,有效长度50cm)为分离通道, 20mmol/L硼砂(含体积分数为30%的N, N-二甲基甲酰胺)为运行缓冲液,采用重力进样,进样时间10s,分离电压为20kv,紫外检测波长254nm。
结果:己烯雌酚和双烯雌酚在9min内达到基线分离,在2.0×10-6-2.0×10-4mol/L,2.0×10-6-2.0×10-4mol/L浓度范围内呈良好的线性关系,线性相关系数分别为0.9991、0.9994,检出限为6.7×10~(-7)mol/L和3.3×10~(-7)mol/L,回收率分别在89.6-94.6%和88.7-104.8%之间,相对标准偏差为3.97%和4.54%。
结论:该方法简便、快速、准确,用于市售育发产品中己烯雌酚和双烯雌酚的检测,结果令人满意。
Diethylstilbestrol and dienestrol are synthetic non-steroid phenolic estrogens with similar structures. They are clinically used as supplements for insufficient estrogen and for the treatment of breast cancer, prostatic cancer, amenorrhea and menopausal syndrome. They can also promote the normal development of female genital organs and secondary sexual characters, the propagation of the endometrium, the uterine contraction and the sensitivity to uterus oxytocic hormone. They can stimulate the anterior pituitary to secrete gonodotropin and prolactin in small dosages. However, inhibition effects can be achieved in large dosages. Dienestrol is the in vivo metabolite of diethylstilbestrol. In animal husbandry, diethylstilboestrol and dienestrol are mainly used to increase milk production and promote the synthesis of proteins. They can promote the sedimentation of proteins and reduce the sedimentation of fat. Climacteric disturbance, loss of fertility, sexual precocity in females, feminization in males, breast cancer and oophoroma can be caused after long term use of Stilboestrol and dienestrol or intake of diethylstilboestrol and dienestrol containing milk products or meat products. So it is of high significance to establish convenient and rapid detection methods on Stilboestrol and Dienestrol.
Through large amounts of preliminary studies it has been found that luminol can be oxidized by Ag(Ⅲ) complexes to generate stable chemoluminescence signals in basic media. Some substances can significantly enhance or inhibit the chemoluminescence from luminol-Ag(Ⅲ) complexes. And there is a good linear relation between strength of chemoluminescence and substance concentration within a certain range. In this study we combined a new luminol-Ag(Ⅲ) complex chemoluminescence system and a kind of flow injection technology to establish a new method for the detection of diethylstilboestrol and used this method for the assay of diethylstilboestrol tablets.
Capillary electrophoresis combines electrophoretic technologies and modern microcolumn separation technologies. With high voltage direct current electric field as the drive, highly efficient and rapid separation can be achieved in capillaries according to different mobility and distribution behaviors of different components. The separation channels for capillary electrophoresis are hollow capillaries. The requirements on pre-treatment of samples are low. The purpose of this study is to establish a capillary electrophoresis method for the detection of Stilboestrol and Dienestrol in hair growth promotion products.
PART 1 Detection of diethylstilboestrol content in diethylstilboestrol tablets with a new flow injection - Ag(Ⅲ) - Luminol chemoluminescence system
Objective: To establish a detection of diethylstilboestrol content in diethylstilboestrol tablets with a novel flow injection - Ag(Ⅲ) - Luminol chemoluminescence system.
Methods: In alkaline medium, a novel flow injection injection - Ag(Ⅲ) - Luminol chemiluminescent method has been developed for the determination of diethylstilbestrol, based on the inhibition of diethystilbestol on the chemiluminescence reaction between luminol and Ag(III) coordination compounds, and the chemiluminescent intensity show good linearity to the concentration of the analytes within a certain range. Conditions of this chemiluminescent reaction have been systematically investigated and optimized. And this method has been applied for the determination of diethylstilbestrol in diethylstilbestrol tablet.
Results: A novel flow injection - Ag(Ⅲ) - Luminol chemoluminescence system for determination of diethylstilbestrol was developed. The detection limit was 3.0×10~(-7) mol/L. The linear equation of the method was△I=5.84×10~8C+548, r =0.9989, the recoveries of standard addition was in rang of 88.6%-94.0% . The relative standard deviation was 3.4% for 1.0×10~(-5) mol/L of diethylstilbestrol (n=7).
Conclusions: The novel flow injection - Ag(Ⅲ) - Luminol chemoluminescence system can be applied for the determination of diethylstilbestrol in diethylstilbestrol tablet . The method is simple, fast, accurate and reliable. It can be used for fast quality control in process of pharmaceutical production.
PART 2 Determination of diethylstilbestrol and dienestrol in hair growth product by capillary electrophoresis
Objective: To establish a new method for determination of diethylstilbestrol and dienestrol in hair growth product by capillary electrophoresis with UV detection.
Methods: An uncoated fused-silica capillary column (75μm i.d.×55 cm, effective length 50 cm) was used as separation channel. The running buffer contained 20mmol/L borate with additive of 30% (by volume) N,N-Dimethylformamide. A constant voltage of 20 kV was applied and the UV detector was set at 254 nm. Samples were injected by gravity for 10 s.
Results: A good baseline separation of diethylstilbestrol and dienestrol was obtained with in 9 min. The calibration curves were linear in the range of 2.0×10~(-6)-2.0×10~(-4)mol/L for diethylstilbestrol and 2.0×10~(-6)-2.0×10~(-4)mol/L for dienestrol, with linear correlation coefficients of 0.9991 and 0.9994, respectively. The limits of detection of diethylstilbestrol and dienestrol were 6.7×10~(-7)mol/L and 3.3×10~(-7)mol/L, respectively. The average recovery of diethylstilbestrol and dienestrol were between 89.6-94.6% and 88.7-104.8%, with the relative standard deviation (RSD) of 3.97% and 4.54%.
Conclusion: The method is simple, convenient and sensitive, which is suitable for determination of diethylstilbestrol and dienestrol residues in hair growth product.
在碱性介质中,Ag(Ⅲ)配合物氧化鲁米诺产生稳定的化学发光信号,某些物质能显著增强或抑制鲁米诺-Ag(Ⅲ)体系的化学发光,并且发光强度与物质浓度在一定范围内呈良好的线性关系。本试验将Ag(Ⅲ)-鲁米诺化学发光新体系与流动注射技术相结合,建立了检测己烯雌酚的新方法,并将此方法应用于己烯雌酚片剂的含量测定。毛细管电泳将电泳技术与现代微柱分离技术相结合,以高压直流电场为驱动力,在毛细管中按各组分的淌度和分配行为的不同进行高效、快速的分离。毛细管电泳的分离通道为中空的毛细管,对样品的预处理要求较低,本研究旨在建立毛细管电泳法测定育发产品中己烯雌酚和双烯雌酚。
一、流动注射-Ag(Ⅲ)-鲁米诺化学发光新体系测定己烯雌酚片剂中己烯雌酚含量
目的:建立流动注射-Ag(Ⅲ)-鲁米诺化学发光新体系测定己烯雌酚片剂中己烯雌酚含量的新方法。
方法:在碱性条件下,鲁米诺被Ag(Ⅲ)氧化产生稳定的化学发光信号,己烯雌酚能显著抑制Ag(Ⅲ)-鲁米诺体系的化学发光作用,且发光强度与样品的浓度在一定范围内呈良好的线性关系。通过对鲁米诺溶液浓度、碱度和Ag(Ⅲ)溶液浓度、碱度等一系列发光条件进行优化选取,在最佳发光条件下绘制己烯雌酚的标准曲线,并对样品进行含量测定。
结果:流动注射-化学发光法测定己烯雌酚的最低检出限为3.0×10~(-7) mol/L。线性范围为5.0×10~(-7)-5.0×10~(-5) mol/L ,回归方程为△I=5.84×10~8C+548,线性相关系数r=0.9989。对1.0×10~(-5) mol/L的己烯雌酚连续进行平行测定7次,RSD为3.4%,加标回收率在88.6%-100.0%之间,RSD为3.7%。
结论:流动注射化学发光法测定己烯雌酚片剂中己烯雌酚含量,方法简便快捷、准确可靠,可用于己烯雌酚片剂生产过程己烯雌酚的质量控制。
二、毛细管电泳法测定育发产品中的己烯雌酚和双烯雌酚
目的:建立毛细管电泳-紫外检测法测定育发产品己烯雌酚和双烯雌酚含量的新方法。
方法:采用未涂层弹性熔融石英毛细管(75μm i.d.×55 cm,有效长度50cm)为分离通道, 20mmol/L硼砂(含体积分数为30%的N, N-二甲基甲酰胺)为运行缓冲液,采用重力进样,进样时间10s,分离电压为20kv,紫外检测波长254nm。
结果:己烯雌酚和双烯雌酚在9min内达到基线分离,在2.0×10-6-2.0×10-4mol/L,2.0×10-6-2.0×10-4mol/L浓度范围内呈良好的线性关系,线性相关系数分别为0.9991、0.9994,检出限为6.7×10~(-7)mol/L和3.3×10~(-7)mol/L,回收率分别在89.6-94.6%和88.7-104.8%之间,相对标准偏差为3.97%和4.54%。
结论:该方法简便、快速、准确,用于市售育发产品中己烯雌酚和双烯雌酚的检测,结果令人满意。
Diethylstilbestrol and dienestrol are synthetic non-steroid phenolic estrogens with similar structures. They are clinically used as supplements for insufficient estrogen and for the treatment of breast cancer, prostatic cancer, amenorrhea and menopausal syndrome. They can also promote the normal development of female genital organs and secondary sexual characters, the propagation of the endometrium, the uterine contraction and the sensitivity to uterus oxytocic hormone. They can stimulate the anterior pituitary to secrete gonodotropin and prolactin in small dosages. However, inhibition effects can be achieved in large dosages. Dienestrol is the in vivo metabolite of diethylstilbestrol. In animal husbandry, diethylstilboestrol and dienestrol are mainly used to increase milk production and promote the synthesis of proteins. They can promote the sedimentation of proteins and reduce the sedimentation of fat. Climacteric disturbance, loss of fertility, sexual precocity in females, feminization in males, breast cancer and oophoroma can be caused after long term use of Stilboestrol and dienestrol or intake of diethylstilboestrol and dienestrol containing milk products or meat products. So it is of high significance to establish convenient and rapid detection methods on Stilboestrol and Dienestrol.
Through large amounts of preliminary studies it has been found that luminol can be oxidized by Ag(Ⅲ) complexes to generate stable chemoluminescence signals in basic media. Some substances can significantly enhance or inhibit the chemoluminescence from luminol-Ag(Ⅲ) complexes. And there is a good linear relation between strength of chemoluminescence and substance concentration within a certain range. In this study we combined a new luminol-Ag(Ⅲ) complex chemoluminescence system and a kind of flow injection technology to establish a new method for the detection of diethylstilboestrol and used this method for the assay of diethylstilboestrol tablets.
Capillary electrophoresis combines electrophoretic technologies and modern microcolumn separation technologies. With high voltage direct current electric field as the drive, highly efficient and rapid separation can be achieved in capillaries according to different mobility and distribution behaviors of different components. The separation channels for capillary electrophoresis are hollow capillaries. The requirements on pre-treatment of samples are low. The purpose of this study is to establish a capillary electrophoresis method for the detection of Stilboestrol and Dienestrol in hair growth promotion products.
PART 1 Detection of diethylstilboestrol content in diethylstilboestrol tablets with a new flow injection - Ag(Ⅲ) - Luminol chemoluminescence system
Objective: To establish a detection of diethylstilboestrol content in diethylstilboestrol tablets with a novel flow injection - Ag(Ⅲ) - Luminol chemoluminescence system.
Methods: In alkaline medium, a novel flow injection injection - Ag(Ⅲ) - Luminol chemiluminescent method has been developed for the determination of diethylstilbestrol, based on the inhibition of diethystilbestol on the chemiluminescence reaction between luminol and Ag(III) coordination compounds, and the chemiluminescent intensity show good linearity to the concentration of the analytes within a certain range. Conditions of this chemiluminescent reaction have been systematically investigated and optimized. And this method has been applied for the determination of diethylstilbestrol in diethylstilbestrol tablet.
Results: A novel flow injection - Ag(Ⅲ) - Luminol chemoluminescence system for determination of diethylstilbestrol was developed. The detection limit was 3.0×10~(-7) mol/L. The linear equation of the method was△I=5.84×10~8C+548, r =0.9989, the recoveries of standard addition was in rang of 88.6%-94.0% . The relative standard deviation was 3.4% for 1.0×10~(-5) mol/L of diethylstilbestrol (n=7).
Conclusions: The novel flow injection - Ag(Ⅲ) - Luminol chemoluminescence system can be applied for the determination of diethylstilbestrol in diethylstilbestrol tablet . The method is simple, fast, accurate and reliable. It can be used for fast quality control in process of pharmaceutical production.
PART 2 Determination of diethylstilbestrol and dienestrol in hair growth product by capillary electrophoresis
Objective: To establish a new method for determination of diethylstilbestrol and dienestrol in hair growth product by capillary electrophoresis with UV detection.
Methods: An uncoated fused-silica capillary column (75μm i.d.×55 cm, effective length 50 cm) was used as separation channel. The running buffer contained 20mmol/L borate with additive of 30% (by volume) N,N-Dimethylformamide. A constant voltage of 20 kV was applied and the UV detector was set at 254 nm. Samples were injected by gravity for 10 s.
Results: A good baseline separation of diethylstilbestrol and dienestrol was obtained with in 9 min. The calibration curves were linear in the range of 2.0×10~(-6)-2.0×10~(-4)mol/L for diethylstilbestrol and 2.0×10~(-6)-2.0×10~(-4)mol/L for dienestrol, with linear correlation coefficients of 0.9991 and 0.9994, respectively. The limits of detection of diethylstilbestrol and dienestrol were 6.7×10~(-7)mol/L and 3.3×10~(-7)mol/L, respectively. The average recovery of diethylstilbestrol and dienestrol were between 89.6-94.6% and 88.7-104.8%, with the relative standard deviation (RSD) of 3.97% and 4.54%.
Conclusion: The method is simple, convenient and sensitive, which is suitable for determination of diethylstilbestrol and dienestrol residues in hair growth product.
引文
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8赵同刚.化妆品卫生规范.军事医学出版社,2007年3月
9许泓,国芳,林安清,等.动物组织中多种残留非类固醇同化激素的液相色谱-串联质谱法同时测定.分析测试学报,2007,26(6):837 - 840
10张红英,张宏,王淑惠,等.气相色谱-质谱法测定牛奶中的8种环境雌激素和内源性雌激素.中国卫生检验杂志,2009,19(8):1713-1715
11 Lesslie C Dickson, James D Macneil, Joann Reid, et al. Validation of Screening Method for Residues of Diethylstilbestrol, Dienestrol, Hexetrol, and Zeranol in Bovine Urine Using Immunoaffinity Chromatography and Gas Chromatography/Mass Spectrometry. J AOAC inter, 2003, 86 (4):631 - 639
12林奕芝,张世英,梁伟,等.HPLC法同时测定肉与肉制品中沙丁胺醇和8种雌激素残留量.公共卫生,2002,18(12):1499-1501
13刘宏程,邹红艳,黎其万,等.高效液相色谱分离牛奶中己烯雌酚、己烷雌酚和双烯雌酚.分析化学研究简报,2008,36(2):245-248
14韩见龙,于村,葛乐瑶,等.毛细管气相色谱法测定肉类食品中游离己烯雌酚的残留量.中国卫生检验杂志,2004,14(6):726-728
15周艳明,牛森.气相色谱法测定肉中己二烯雌酚残留量.中国食品卫生杂志,2006,5:420-421
16柳爱春,刘超,徐晓丹,等.水产品中己烯雌酚快速检测方法试验分析.现代农业科技,2009,(15):353-354
17 HOFFMANN B, WELER S. Radioimmunological determination of stilbene residues in tissue samples from pigs. Archiv-Fur-Lebensm Ittelhygiene, 1986,37(6):137-142
18林子俺,庞纪磊,黄慧,等.水产品中己烷雌酚、己烯雌酚与双烯雌酚残留的毛细管电泳测定.分析测试学报,2010,29(1):55-58
1樊官伟,何俊,王虹,等.雌激素及其受体信号转到途径的研究进展.中国临床药理学与治疗学,2007,12(3):266-269
2 Catherine M, Jacqueline G, Marie-Christine L, et al. Analytical performaance of a new two-step ADVIA centaur estradiol immunoassay during ovarian stimulation. Clin Chen Lab Med, 2006,44(1):105-109
3赵怀鑫,孙志伟,夏莲,等.新型荧光衍生试剂用于尿样中痕量游离雌二醇和雌三醇的反相高效液相色潽-荧光检测和质谱定性.色谱,2009,27(2):164-168
4吴鸳鸯,施卫星,陈枢青.GC/MS同时检测人体尿液中β-雌二醇、双酚A、己烯雌酚和沙丁胺醇的含量.浙江大学学报,2009,38(3):235-241
5魏慧斌,林金明,吴丹凝,等.水体及人体液中雌二醇的高灵敏度化学发光酶免疫分析.分析化学,2007,35(3):320-324
6李静,赵刚,苏庆,等.高效液相色谱法测定聚乙二醇单甲醚-聚D,L-乳酸微球中雌二醇的含量.中国医院药学杂志,2010,30(23):2038-2039
7 Tagawa N, Tsuruta H, Fujinami A, et al. Simultaneous Determination of Estriol and Striol 3-Sulfate in Serum by Column-Switching Semi-Micro High-Performance Liquid Chromatography with Ultraviolet and Electrochemical Detection. Journal of Chromatography B, 1999,723(1-2):39-45
8毛丽莎,孙成,李永新,等.柱前荧光衍生-高效液相色谱法测定尿和血清中的环境雌激素.分析化学,2005,33(1):33-36
9 Leis H J, Fauler G, Rechberger G N, et al. Quantitative Trace Analysis of Estriol in Human Plasma by Negative Ion Chemical Ionization Gas Chromatography-Mass Spectrometry Using a Deuterated Internal Standaard. Journal of Chromatography B, 2003,794(2):205-203
10刘勇军,吴银良,姜艳彬,等.固相萃取气相色谱-质谱联用法测定牛奶中的雌三醇.中国乳品工业,2006,34(11):47-49
11高素芹,杜凌云,王术皓.基于固相抗体模式时间分辨荧光免疫分析测定雌三醇.光谱实验室,2010,27(3):1089-1093
12钱建瑞,赵艳伟,梁艳,等.量子点标记链霉亲和素荧光免疫分析测定雌三醇.分析实验室,2009,28(6):104-107
13蒋艺勤,汤永平,丁岚,等.游离雌三醇时间分辨免疫荧光分析法的建立.热带医学,2007,7(3):212-214
14 Ius A, Ferrara L, Meroni G, et al. Direct Time-Resolved Fluoroimmunoassary of Estriol in Serum. J. Steriod Biochem. Molec. Biol., 1991,39(2):189-192
15苏萍,王永成,张新祥,等.毛细管电泳免疫分析法分析雌三醇.分析化学,2003,31(4):385-388
16 Heizman R J, Report Eur. 15126-EN Published on Behalf of European Communities. 1994,24
17罗晓燕,林玉娜,刘莉治,等.SPE-HPLC同时测定水产品中己烯雌酚、甲基睾酮的研究.现代预防医学,2005,28(4):287-289
18 Chae K, Lindzey J, McLachlan J A, Korach K S. Steroids, 1998,63(3):149-157
19 Giusti RM, Iwamoto K, Hatch EE. Diethylstibestrol revisited a review of the long term health effects. Ann Inter M ed, 1995,122:778-788
20 Hansen J. Breast cancer risk among relatively young women employed in solvent using industries. Am J Ind Med, 1999,36:43-47
21 Clbrom T, Vom Seal F S, Soto A M. Environ Health Persect, 1993,101(5):378-385
22中华人民共和国农业部第193号公告.《食品动物禁用的兽药及其它化合物清单》,2002,4
23吴银良,刘素英,单吉浩,等.气相色谱-质谱法分析鸡肝中己烯雌酚残留量.中国兽药杂志,2005,39(11):8-10
24孙梅梅,赵艳伟,梁艳,等.荧光免疫法测定鸡肉中己烯雌酚残留.理化检验-化学分册,2010,46(5):465-467
25马纪伟.鸡肉中己烯雌酚残留量的HPLC法测定研究,现代预防医学,2009,36(17):3335-3336
26 Laitem L, Gaspar P, Belb I. Stable Derivatives for the Gas Chromatographic Determination of Synthetic Anabolic Stibene Residues(Diethylstilbestrol, Dienestrol, Hexestrol) in Meat and Organs of Treated Cattle in the Sub-parts Per Billion (10-9) Level. J Chromatogr, 1978,156(2):267-273
27 Martin Y.Determination of Three Anabolic Compounds in Calf Urine by Liquid Chromatography with Photodiode-array Detection. Analyst, 2000,125:2230-2235
28 Casademont G, B Perez, J A Garcia Reguetion. Simultaneous Determination, in Calf Urine, of Twele Anabolic Agents as Heptafluorobutyryl Derivatives by Capillary Gas Chromatography-Mass Spectrometry. Journal of Chromatography B,1996,686:189-198
29应永飞,朱聪英,陈慧华,等.液相色谱-串联质谱法测定动物组织中1,2-二苯乙烯类药物残留的研究.质谱学报,2008,2(6):343-348
30刘宏程,邹艳红,黎其万,等.高效液相色谱分离牛奶中己烯雌酚、己烷雌酚和双烯雌酚.分析化学研究简报,2008,36(2):245-248
31林子俺,庞继磊,黄慧,等.水产品中己烷雌酚、己烯雌酚与双烯雌酚残留的毛细管电泳测定.分析测试学报,2010,29(1):55-58
32王君,周志荣,林少彬.化妆品中6种雌激素的液相色谱串联质谱检测方法研究.卫生研究,2010,39(3):383-385
33 Schonfelder G, Wittfoht W, Hopp H, et al. Parent bisphenol A accumulation in the human maternal-fetal-placental unit. Environ Health Perspect, 2002,110(11):703-707
34张建江,舒为群.邻苯二甲酸酯雌性生殖毒性研究进展.卫生研究,2005,34(4):496-498
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36黄朝晖,郝加虎,陶芳标.环境内分泌干扰物与尿道下裂关系研究进展.中国公共卫生,2009,25(3):371-372
37朱建如,宋毅.环境激素及对人体的危害.公共卫生与预防医学,2006,17(6):38-40
38赵美萍,李元宗,常文保.酚类环境雌激素的分析研究进展.分析化学,2003,31(1):103-109
39 Hooper S W, Pettigrew C A, Sayle G S. Ecological fate, effects and prospects for elimination of environmental polychlorinated biphenyls. Environ Toxicol Chem, 1990,9:655-667
40肖晶,邵兵,吴永宁,等.HPLC-FL法检测尿液中类雌激素双酚A和烷基酚.中国食品卫生杂志,2008,20(2):111-114
41张红英,张宏,王淑惠,等.气相色谱-质谱法测定牛奶中的8种环境激素和内源性雌激素.中国卫生检验杂志,2009,19(8):1713-1715
42徐英江,田秀慧,张秀珍,等.超高效液相色谱串联质谱法对水产品种8种雌激素的测定.分析测试学报,2010,29(2):152-156
43 Zhao M P, Li Z Y,Guo Z Q,et al.A new comptitive enzyme linked immunosorben assay for determination of estrogenic bisphenols. Talanta, 2002,57:1205-1210
44张立科,张艳鸽,何琴.固相萃取富集-化学发光法测定水环境中痕量双酚A.化学试剂,2010,32(4):334-336
2陈杖榴,杨桂香,孙永学.兽药残留的毒性与生态毒理研究进展.华南农业大学学报,2001,22(1):88-91
3 Colbrom T, Vom Seal F S, Soto A M. Environ Health Perspect, 1993,101(5):378-385
4 Wozniak B, Wojton B. Bulletin of the veterinary institute in pulawy. 1996,40(1):55-59
5刘宏程,邹艳红,黎其万,等.高效液相色谱分离牛奶中己烯雌酚、己烷雌酚、和双烯雌酚,分析化学,2008,36(2):245-248
6中华人民共和国农业部发布《2003年度动物性产品中兽药残留监控计划》(农牧发[2003]6号,2003年4月4日)
7 Philip F., Kevin N. A., Anthony C.C., et al. Analytical applications of flow injection with chemiluminescence detection-a review. Luminescence, 2001,16 (1):1-23
8匡佩琳,李平,罗晓红,等.HPLC法测定己烯雌酚软膏含量.药物分析杂志,2000,20(5):351-352
9马纪伟.鸡肉中己烯雌酚残留量的HPLC法测定.现代预防医学,2009,36(17):3335-3336
10林奕芝,张世英,梁伟,等.HPLC法同时测定肉与肉制品中沙丁胺醇和8种雌激素残留量.公共卫生,2002,18(12):1499-1501
11 COFFIN D E, PILON J C. Gas chromatographic determination of diethystilbestrol residues in animal tissues, AOAC, 1973,56(2):352-357
12韩见龙,于村,葛乐瑶,等.毛细管气相色谱法测定肉类食品中游离己烯雌酚的残留量.中国卫生检验杂志,2004,14(6):726-728
13丁雅韵,徐晓云,谢孟峡,等.动物组织中己烯雌酚残留的基体固相扩散-气相色谱-质谱分析方法研究.分析化学,2003,31(11):1356-1359
14郭志峰,安秋荣,刘鹏岩.鸡蛋中己烯雌酚的GC/MS法分析测定,1997,18(3):36-40
15杜志峰,黄金凤,郭新东,等.动物组织中己烯雌酚残留量的液相色谱-串联质谱法测定,分析测试学报,2007,26(6):823-826
16胡鲲,杨先乐,张菊.酶联免疫法检测中华鳖肌肉中己烯雌酚,上海水产大学学报,2002,11(3):199-202
17柳爱春,刘超,徐晓丹,等.水产品中己烯雌酚快速检测方法试验分析.现代农业科技,2009,(15):353-354
18林培英,武向锋,刘荔荔,等.毛细管区带电泳法测定己烯雌酚片剂中己烯雌酚的含量,药物实践杂志,2002,20(5):289-290
19 Shi H.,Xu X., Ding Y., et al .Determination of cortisol in human blood sera by a new Ag(III) complex-luminol chemiluminescent system. Analytical Biochemistry, 2009,387:178-183
1陈义.毛细管电泳技术及应用.化学工业出版社,2000年9月
2陈达灿,榻国维.皮肤性病专科中医临床诊治.人民卫生出版社,2005年2月
3 Sinclair R.Fortnighty review: Male pattern androgenetic alopecia. BMJ,1998,317(7162):865
4 Shapiro J, Price V H. Hair regrowth. Therapeutic agents. Dermatol clin,1998,16(2):341
5陈修漾,陈大灿.不同证候的雄激素性脱发患者受损头皮的病理特征及雄激素受体的表达规律.广州中医药大学学报,2004(213):169-173
6 Colbrom T, Vom Seal F S, Soto A M. Environ Health Perspect, 1993,101(5):378-385
7中华人民共和国农业部发布《2003年度动物性产品中兽药残留监控计划》(农牧发[2003]6号,2003年4月4日)
8赵同刚.化妆品卫生规范.军事医学出版社,2007年3月
9许泓,国芳,林安清,等.动物组织中多种残留非类固醇同化激素的液相色谱-串联质谱法同时测定.分析测试学报,2007,26(6):837 - 840
10张红英,张宏,王淑惠,等.气相色谱-质谱法测定牛奶中的8种环境雌激素和内源性雌激素.中国卫生检验杂志,2009,19(8):1713-1715
11 Lesslie C Dickson, James D Macneil, Joann Reid, et al. Validation of Screening Method for Residues of Diethylstilbestrol, Dienestrol, Hexetrol, and Zeranol in Bovine Urine Using Immunoaffinity Chromatography and Gas Chromatography/Mass Spectrometry. J AOAC inter, 2003, 86 (4):631 - 639
12林奕芝,张世英,梁伟,等.HPLC法同时测定肉与肉制品中沙丁胺醇和8种雌激素残留量.公共卫生,2002,18(12):1499-1501
13刘宏程,邹红艳,黎其万,等.高效液相色谱分离牛奶中己烯雌酚、己烷雌酚和双烯雌酚.分析化学研究简报,2008,36(2):245-248
14韩见龙,于村,葛乐瑶,等.毛细管气相色谱法测定肉类食品中游离己烯雌酚的残留量.中国卫生检验杂志,2004,14(6):726-728
15周艳明,牛森.气相色谱法测定肉中己二烯雌酚残留量.中国食品卫生杂志,2006,5:420-421
16柳爱春,刘超,徐晓丹,等.水产品中己烯雌酚快速检测方法试验分析.现代农业科技,2009,(15):353-354
17 HOFFMANN B, WELER S. Radioimmunological determination of stilbene residues in tissue samples from pigs. Archiv-Fur-Lebensm Ittelhygiene, 1986,37(6):137-142
18林子俺,庞纪磊,黄慧,等.水产品中己烷雌酚、己烯雌酚与双烯雌酚残留的毛细管电泳测定.分析测试学报,2010,29(1):55-58
1樊官伟,何俊,王虹,等.雌激素及其受体信号转到途径的研究进展.中国临床药理学与治疗学,2007,12(3):266-269
2 Catherine M, Jacqueline G, Marie-Christine L, et al. Analytical performaance of a new two-step ADVIA centaur estradiol immunoassay during ovarian stimulation. Clin Chen Lab Med, 2006,44(1):105-109
3赵怀鑫,孙志伟,夏莲,等.新型荧光衍生试剂用于尿样中痕量游离雌二醇和雌三醇的反相高效液相色潽-荧光检测和质谱定性.色谱,2009,27(2):164-168
4吴鸳鸯,施卫星,陈枢青.GC/MS同时检测人体尿液中β-雌二醇、双酚A、己烯雌酚和沙丁胺醇的含量.浙江大学学报,2009,38(3):235-241
5魏慧斌,林金明,吴丹凝,等.水体及人体液中雌二醇的高灵敏度化学发光酶免疫分析.分析化学,2007,35(3):320-324
6李静,赵刚,苏庆,等.高效液相色谱法测定聚乙二醇单甲醚-聚D,L-乳酸微球中雌二醇的含量.中国医院药学杂志,2010,30(23):2038-2039
7 Tagawa N, Tsuruta H, Fujinami A, et al. Simultaneous Determination of Estriol and Striol 3-Sulfate in Serum by Column-Switching Semi-Micro High-Performance Liquid Chromatography with Ultraviolet and Electrochemical Detection. Journal of Chromatography B, 1999,723(1-2):39-45
8毛丽莎,孙成,李永新,等.柱前荧光衍生-高效液相色谱法测定尿和血清中的环境雌激素.分析化学,2005,33(1):33-36
9 Leis H J, Fauler G, Rechberger G N, et al. Quantitative Trace Analysis of Estriol in Human Plasma by Negative Ion Chemical Ionization Gas Chromatography-Mass Spectrometry Using a Deuterated Internal Standaard. Journal of Chromatography B, 2003,794(2):205-203
10刘勇军,吴银良,姜艳彬,等.固相萃取气相色谱-质谱联用法测定牛奶中的雌三醇.中国乳品工业,2006,34(11):47-49
11高素芹,杜凌云,王术皓.基于固相抗体模式时间分辨荧光免疫分析测定雌三醇.光谱实验室,2010,27(3):1089-1093
12钱建瑞,赵艳伟,梁艳,等.量子点标记链霉亲和素荧光免疫分析测定雌三醇.分析实验室,2009,28(6):104-107
13蒋艺勤,汤永平,丁岚,等.游离雌三醇时间分辨免疫荧光分析法的建立.热带医学,2007,7(3):212-214
14 Ius A, Ferrara L, Meroni G, et al. Direct Time-Resolved Fluoroimmunoassary of Estriol in Serum. J. Steriod Biochem. Molec. Biol., 1991,39(2):189-192
15苏萍,王永成,张新祥,等.毛细管电泳免疫分析法分析雌三醇.分析化学,2003,31(4):385-388
16 Heizman R J, Report Eur. 15126-EN Published on Behalf of European Communities. 1994,24
17罗晓燕,林玉娜,刘莉治,等.SPE-HPLC同时测定水产品中己烯雌酚、甲基睾酮的研究.现代预防医学,2005,28(4):287-289
18 Chae K, Lindzey J, McLachlan J A, Korach K S. Steroids, 1998,63(3):149-157
19 Giusti RM, Iwamoto K, Hatch EE. Diethylstibestrol revisited a review of the long term health effects. Ann Inter M ed, 1995,122:778-788
20 Hansen J. Breast cancer risk among relatively young women employed in solvent using industries. Am J Ind Med, 1999,36:43-47
21 Clbrom T, Vom Seal F S, Soto A M. Environ Health Persect, 1993,101(5):378-385
22中华人民共和国农业部第193号公告.《食品动物禁用的兽药及其它化合物清单》,2002,4
23吴银良,刘素英,单吉浩,等.气相色谱-质谱法分析鸡肝中己烯雌酚残留量.中国兽药杂志,2005,39(11):8-10
24孙梅梅,赵艳伟,梁艳,等.荧光免疫法测定鸡肉中己烯雌酚残留.理化检验-化学分册,2010,46(5):465-467
25马纪伟.鸡肉中己烯雌酚残留量的HPLC法测定研究,现代预防医学,2009,36(17):3335-3336
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