盐酸环丙沙星检测新方法研究
摘要
在抗生素领域内,喹诺酮类是唯一可以与内酰胺类抗生素相媲美的合成抗菌药,其对大多数敏感菌有快速杀灭作用。环丙沙星是第三代喹诺酮类药物在临床医学中最成功地得到广泛应用的抗生素之一,具有广谱、高效、低毒以及口服吸收完全、体内分布广、不易产生抗药性等特点,是目前最佳的抗感染药物之一。
本论文建立了三种测定盐酸环丙沙星的新方法,这些方法不仅可以用于评价环丙沙星药物的重要药效指标之一——药物成分的含量,而且对分析食品和环境样品中的环丙沙星药物残留具有参考价值。论文的主要内容如下:
一吖啶橙-罗丹明B能量转移荧光猝灭法测定盐酸环丙沙星
研究了吖啶橙(AO)与罗丹明B(RB)的共振荧光能量转移作用。研究表明,在λex/λem = 470/576 nm,十二烷基硫酸钠存在下,吖啶橙与罗丹明B能够发生有效共振荧光能量转移。盐酸环丙沙星的加入,使得能量转移体系中罗丹明B的荧光猝灭,以此建立了荧光共振能量转移法测定盐酸环丙沙星的新方法。盐酸环丙沙星含量在0.02-0.44μg/mL范围内,罗丹明B的荧光猝灭程度与盐酸环丙沙星的浓度呈良好的线性关系,回归方程为:△F = 378.0c (μg/mL) + 11.14,相关系数r = 0.9966,最低检出限为0.013μg/mL。此法用于测定盐酸环丙沙星滴眼液的测定,并与国家标准方法高效液相色谱法相比较,结果一致。
二刚果红褪色光度法测定盐酸环丙沙星
在弱酸性Britton-Robinson缓冲介质中,盐酸环丙沙星与刚果红染料反应,形成离子缔合物,溶液吸光度明显降低,最大褪色波长在496 nm处,据此建立了测定盐酸环丙沙星的褪色光度法。当CPFX浓度在0.8 ~ 8.0 mg/L范围内时,褪色程度△A与CPFX浓度间呈现良好的线性关系,其线性回归方程为:△A=0.03257c(mg/L)-0.0245,相关系数R=0.9980,最低检出限为0.3376 mg/L。此法用于环丙沙星药物的测定,并与国家标准方法高效液相色谱法相比较,结果令人满意。
三环丙沙星(CPFX)-锌(Ⅱ)的配合性能及环丙沙星的含量测定
本文研究了环丙沙星(CPFX)-锌(Ⅱ)的配合反应,通过摩尔比法求得了配合物的配比为2:1,计算了配合物的离解度和稳定常数。并且研究发现,锌离子与环丙沙星配合后,使体系的紫外吸收有一定程度提高,据此建立了一个新的测定环丙沙星含量的方法。对环丙沙星药物制剂进行测定,结果令人满意。
In the antibiotics family, quinolones antibiotics are the only kind synthesis antibacterial drugs which can compare beauty with lactam kind antibiotics. They have the fast sterilization effect for most sensitive bacteria. Ciprofloxacin are widely applied to the clinical medicine as one of the most successful third generation quinolones drugs. Due to many characteristics such as broad spectrum, efficient, low toxicity and complete oral absorption, wide distribution, hard to cause drug-resistance, Ciprofloxacin has been one of the best anti-infective drugs at present.
In the present study, three new analytical methods for the determination of ciprofloxacin hydrochloride were developed. These methods are not only used to evalue the effective component which is as one of the most imporment pharmacodynamics indexes, but applicable in the analysis of pharmaceutical residues like antibodies in environment samples as well as in foods. The major results of the
present study are listed as below:
1. A fluorescence quenching method for the determination of ciprofloxacin hydrochloride by fluorescence resonance energy transfer between acridine orange and rhodamine B
The fluorescence resonance energy transfer between acridine orange and rhodamine B has been studied. It was found that the effective energy transfer occurred between acridine orange and rhodamine B in the sodium dodecyl sulfate atλex /λem = 470 / 576 nm and Britton-Robinson buffer(pH = 7.0). The fluorescence intensity of rhodamine B which had increased sharply in the energy transfer system was regularly diminished by ciprofloxacin hydrochloride, and the quenching fluorescence intensity showed a good linear relationship with the concentration of ciprofloxacin hydrochloride in the range of 0.02 to 0.44μg/mL. The equation of linear regression was△F = 378.0c(μg/mL) + 11.14(correlation coefficient r = 0.9966), the detection limit was found to be 0.013μg/mL. The method was applied to the determination of ciprofloxacin in ciprofloxacin hydrochloride eye drops. It was validated applying the standard addition methodology and using HPLC as a reference method.
2. Fading spectrophotometric method for determination of Ciprofloxacin Hydrochloride with Congo Red
In weak acidic of Britton-Robinson buffer medium, ciprofloxacin hydrochloride reacts with Congo Red to form an ion-association complex,and the absorption of Congo Red decreases obviously.The maximum fading wavelength at 496nm.Based on this reaction, a new fading spectrophotometric method was developed for determination of ciprofloxacin hydrochloride. The equation of linear regression was△A=0.03257c(mg/L)-0.0245 (correlation coefficient r = 0.9980) in the range of ciprofloxacin hydrochloride concentration in 0.8—8.0mg/L, the detection limit was found to be 0.3376 mg/L.The method was applied to the determination of ciprofloxacin drugs with good results.
3. Complexation characteristics of ciprofloxacin with Zn(Ⅱ)and determination of ciprofloxacin
The complexation characteristics of ciprofloxacin(CPFX) with Zn(Ⅱ)has been studied. The complexing ratio of the complex has been determined to be 2:1 using molar ratio method,and the degree of dissociation and stability constant were calculated. Based on this complex reaction, a simple, rapid and sensitive new method for the UV determination of CPFX was proposed and the reaction conditions were investigated in detail. The method was applied to the determination of ciprofloxacin drugs with good results.
本论文建立了三种测定盐酸环丙沙星的新方法,这些方法不仅可以用于评价环丙沙星药物的重要药效指标之一——药物成分的含量,而且对分析食品和环境样品中的环丙沙星药物残留具有参考价值。论文的主要内容如下:
一吖啶橙-罗丹明B能量转移荧光猝灭法测定盐酸环丙沙星
研究了吖啶橙(AO)与罗丹明B(RB)的共振荧光能量转移作用。研究表明,在λex/λem = 470/576 nm,十二烷基硫酸钠存在下,吖啶橙与罗丹明B能够发生有效共振荧光能量转移。盐酸环丙沙星的加入,使得能量转移体系中罗丹明B的荧光猝灭,以此建立了荧光共振能量转移法测定盐酸环丙沙星的新方法。盐酸环丙沙星含量在0.02-0.44μg/mL范围内,罗丹明B的荧光猝灭程度与盐酸环丙沙星的浓度呈良好的线性关系,回归方程为:△F = 378.0c (μg/mL) + 11.14,相关系数r = 0.9966,最低检出限为0.013μg/mL。此法用于测定盐酸环丙沙星滴眼液的测定,并与国家标准方法高效液相色谱法相比较,结果一致。
二刚果红褪色光度法测定盐酸环丙沙星
在弱酸性Britton-Robinson缓冲介质中,盐酸环丙沙星与刚果红染料反应,形成离子缔合物,溶液吸光度明显降低,最大褪色波长在496 nm处,据此建立了测定盐酸环丙沙星的褪色光度法。当CPFX浓度在0.8 ~ 8.0 mg/L范围内时,褪色程度△A与CPFX浓度间呈现良好的线性关系,其线性回归方程为:△A=0.03257c(mg/L)-0.0245,相关系数R=0.9980,最低检出限为0.3376 mg/L。此法用于环丙沙星药物的测定,并与国家标准方法高效液相色谱法相比较,结果令人满意。
三环丙沙星(CPFX)-锌(Ⅱ)的配合性能及环丙沙星的含量测定
本文研究了环丙沙星(CPFX)-锌(Ⅱ)的配合反应,通过摩尔比法求得了配合物的配比为2:1,计算了配合物的离解度和稳定常数。并且研究发现,锌离子与环丙沙星配合后,使体系的紫外吸收有一定程度提高,据此建立了一个新的测定环丙沙星含量的方法。对环丙沙星药物制剂进行测定,结果令人满意。
In the antibiotics family, quinolones antibiotics are the only kind synthesis antibacterial drugs which can compare beauty with lactam kind antibiotics. They have the fast sterilization effect for most sensitive bacteria. Ciprofloxacin are widely applied to the clinical medicine as one of the most successful third generation quinolones drugs. Due to many characteristics such as broad spectrum, efficient, low toxicity and complete oral absorption, wide distribution, hard to cause drug-resistance, Ciprofloxacin has been one of the best anti-infective drugs at present.
In the present study, three new analytical methods for the determination of ciprofloxacin hydrochloride were developed. These methods are not only used to evalue the effective component which is as one of the most imporment pharmacodynamics indexes, but applicable in the analysis of pharmaceutical residues like antibodies in environment samples as well as in foods. The major results of the
present study are listed as below:
1. A fluorescence quenching method for the determination of ciprofloxacin hydrochloride by fluorescence resonance energy transfer between acridine orange and rhodamine B
The fluorescence resonance energy transfer between acridine orange and rhodamine B has been studied. It was found that the effective energy transfer occurred between acridine orange and rhodamine B in the sodium dodecyl sulfate atλex /λem = 470 / 576 nm and Britton-Robinson buffer(pH = 7.0). The fluorescence intensity of rhodamine B which had increased sharply in the energy transfer system was regularly diminished by ciprofloxacin hydrochloride, and the quenching fluorescence intensity showed a good linear relationship with the concentration of ciprofloxacin hydrochloride in the range of 0.02 to 0.44μg/mL. The equation of linear regression was△F = 378.0c(μg/mL) + 11.14(correlation coefficient r = 0.9966), the detection limit was found to be 0.013μg/mL. The method was applied to the determination of ciprofloxacin in ciprofloxacin hydrochloride eye drops. It was validated applying the standard addition methodology and using HPLC as a reference method.
2. Fading spectrophotometric method for determination of Ciprofloxacin Hydrochloride with Congo Red
In weak acidic of Britton-Robinson buffer medium, ciprofloxacin hydrochloride reacts with Congo Red to form an ion-association complex,and the absorption of Congo Red decreases obviously.The maximum fading wavelength at 496nm.Based on this reaction, a new fading spectrophotometric method was developed for determination of ciprofloxacin hydrochloride. The equation of linear regression was△A=0.03257c(mg/L)-0.0245 (correlation coefficient r = 0.9980) in the range of ciprofloxacin hydrochloride concentration in 0.8—8.0mg/L, the detection limit was found to be 0.3376 mg/L.The method was applied to the determination of ciprofloxacin drugs with good results.
3. Complexation characteristics of ciprofloxacin with Zn(Ⅱ)and determination of ciprofloxacin
The complexation characteristics of ciprofloxacin(CPFX) with Zn(Ⅱ)has been studied. The complexing ratio of the complex has been determined to be 2:1 using molar ratio method,and the degree of dissociation and stability constant were calculated. Based on this complex reaction, a simple, rapid and sensitive new method for the UV determination of CPFX was proposed and the reaction conditions were investigated in detail. The method was applied to the determination of ciprofloxacin drugs with good results.
引文
[1] 权建昌. 抗生素不合理应用分析[J]. 中国社区医师,2006,8(143):4
[2] 周国民. 认识抗生素[J]. 中国保健营养,2004,8:22-23
[3] 姬平,呼慧梅. 滥用抗生素的危害[J]. 中国现代医药杂志,2006, 8(7):39
[4] Bayskier A , Chanto t J-F. Classification and structure and activity relationships of fluoroquinolones[J]. Drugs,1995,49 (Suppl2) :16
[5] 范柏. 喹诺酮类抗菌药的作用机制及细菌耐药性的研究进展[J]. 国外医药抗生素分册,2004,25(1):27-29
[6] 张致平. 喹诺酮类抗菌药研究的新进展[J]. 国外医药抗生素分册, 2001,22(6):241-246
[7] 朱秀美, 张志萍, 郭代红,等. 喹诺酮类抗菌药品不良反应分析[J].中华医院感染学杂志,2001,11(4):306-307
[8] 张健, 王虹. 氟喹诺酮类药致28例不良反应及相关因素的临床分析与研究[J]. 中国民康医学杂志,2003,15(5):278-282
[9] 刘明亮,郭惠元,等. 喹诺酮类抗菌药的概况与展望及研究新进展[J]. 国外医药抗生素分册,2001,22(1):1-4
[10] 柴栋,王春. 氟喹诺酮类抗菌药物所致心肌传导紊乱[J].中国药物应用与监测,2005,5:12-15
[11] 蒋天如,屈健. 环丙沙星致急性间质性肾炎1例[J]. 临床误诊误治,1999,12 (3):222-223.
[12] 包军胜. 环丙沙星致急性肾功能衰竭1例[J]. 医药导报,2000,19(1):31
[13] Hadimeri H , Almroth G, Cederbrandt K, et al . Allergic nephrotoxicity associated with norfloxacin and ciprofloxacin therapy[J]. Scand J Urol Nephrol, 1997,31:4812485.
[14] 宋东奎, 王瑞. 氟喹诺酮类药物致肾脏严重不良反应分析[J]. 中华医院感染学杂志,2003,13(4):371-372
[15] Go ldstein FW,A car JF. Epidemiology of quinolone resistance :Europe and no rth and south America. [J]. Drugs, 1995,49 (Supp l2) :36
[16] Turnidge J. Ep idemiology of quinolone resistance :Eastern hemisphere. [J]. D rugs,1995,49 (Supp l2) :43
[17] 医疗情报.システム开发·ソタ 药剂感受性情报. [R ].东京: 药业时报社, 1993
[18] 张致平. 喹诺酮类抗菌药研究的新进展[J]. 国外医药抗生素分册,2001, 22(6):241-283
[19] http://www.ljzy.com.cn/c2045/c2064/w1600.asp
[20] 刘伟祥. 紫外分光光度法测定0.5%环丙沙星滴眼液的含量[J]. 实用医学杂志,1994,10(7):689
[21] 张慧,洪有采,余珲,等. 紫外分光光度法测定盐酸环丙沙星软膏含量[J]. 中国药房,1995,6(4):38
[22] 武洋,张素范,王沪凯,等. 紫外分光光度法测定双唑星栓中乳酸环丙沙星和甲硝唑的含量[J]. 实用药物与临床,2005,8(2):19-21
[23] M Isabel Pascual-Reguera, Gertrudis Pérez Parras, Antonio Molina Díaz. Solid-phase UV spectrophotometric method for determination of ciprofloxacin[J]. Microchemical Journal,2004,77:79-84
[24] 李之琳,陈贵起. 差示分光光度法测定复方环丙沙星滴眼液中环丙沙星含量[J]. 中国药业,2006,15(1):39
[25] 刘瑞玲,徐景仁,刘友皋,等. 盐酸环丙沙星含量的测定方法研究[J]. 药物分析杂志,1994,14(1):45-46
[26] 王妮. 抗菌可溶性止血纱布中环丙沙星的含量测定[J]. 中国新药杂志,2004,13(5):430-431
[27] 高建华,林鹏,刘钺,等. 荧光法测定乳酸环丙沙星的含量 [J]. 河南化工,1999,2:27-28
[28] 徐子刚,郑琳,吴清洲. 环丙沙星荧光特性的研究[J]. 药物分析杂志,2003(23):41-43
[29] 周采菊,卢宁,郭永恩. 荧光光度法测定盐酸环丙沙星软膏的含量[J]. 药物分析杂志,1998,18(3):200-201
[30] 吴淑清,曹秋娥,赵云昆,等. 铽-环丙沙星体系的荧光特性及环丙沙星的测定[J]. 分析化学,2000,28(12):1462-1466
[31] Michael E. El-Kommos, Gamal A. Saleh, Samia M. El-Gizawi等. Spectrofluorometric determination of certain quinolone antibacterials using metal chelation[J]. Talanta,2003(60):1033-1050
[32] 徐瑞云, 刘璇昕, 孙梅佳,等. 环丙沙星和氧氟沙星的荧光光谱法测定[J]. 上海应用技术学院学报,2005,5(1):4-10
[33] 邵爽. 荧光分析法测定滴眼液和片剂中环丙沙星的含量[J]. 浙江教育学院学报,2004,7(4):70-74
[34] 马文诗,刘树春. 高效液相色谱法测定盐酸环丙沙星滴眼液含量的研究[J]. 天津药学,1995,7(4):70-72
[35] 王康俊,蔡珊英,刘汉山. 高效液相色谱法测定盐酸环丙沙星软膏的含量[J]. 药物分析杂志,2001,21(1):43-44
[36] 白林,魏萍,王瑾. 高效液相色谱法测定复方环丙沙星滴鼻液中3组分含量[J]. 解放军药学学报,2002,18(2):79-81
[37] 符成龙,殷栋二,董荣毛. 高效液相色谱法测定盐酸环丙沙星栓的含量[J]. 中国药业,2004,13(11):40
[38] 黄建凡,陈建华,陈奇. 高效液相色谱法测定环丙沙星片剂的尿药浓度[J]. 抗感染药学,2005,2(3):141-142
[39] 陈烨,周云鹏,檀德宏,等. HPLC法同时测定复方盐酸环丙沙星滴耳液两组分的含量[J]. 辽宁大学学报:自然科学版,2006,33(4):327-330
[40] PREDRAG SIBINOVI?,ANDREJA ?MELCEROVI?, RADOSAV PALI?等. Ruggedness testing of an HPLC method for the determination of ciprofloxacin[J]. J. Serb. Chem. Soc,2005,70 (7) :979–986
[41] 汪秀龄,张淑敏,赫春香. 乳酸环丙沙星单扫描示波极谱法研究 [J]. 高等学校化学学报; 1996年06期; 874-877
[42] 李彦威,林建英,魏文珑,等. Gran 电位滴定法测定乳酸环丙沙星[J]. 分析试验室,2005,24(8):79-81
[43] 杜黎明,王静萍,刘艳红. 环丙沙星荷移反应及荧光光谱性质研究[J]. 分析化学,2002, 30(6):658-660
[44] 连宁,王建朝,冷文红,等. 流动注射化学发光法测定环丙沙星[J]. 光谱学与光谱分析,2005,25(7):1038-1041
[45] 宋雅茹,王尚芝. 火焰原子吸收光谱法测定盐酸环丙沙星[J]. 北京师范大学学报:自然科学版,2002,38(1):80-83
[46] 谢志海,袁红安,常斌,等. 间接原子吸收法测定乳酸环丙沙星[J]. 分析试验室,2003 , 22(1 ):78-80
[47] 李红,任乃林. 荧光光度法测定鱼肉中的环丙沙星[J]. 食品科技,2006,9:245-247
[48] 席会平 董学芝 胡卫平,等. 荧光法快速测定鸡血清中环丙沙星的残留量[J].华西药学杂志,2006,21(3):275-277
[49] 席会平 , 董学芝 , 胡卫平,等. 表面活性剂增敏荧光光度法快速测定残留牛奶中的环丙沙星[J]. 中国抗生素杂志,2006,31(5):285-286,313
[50] 伍冶,操继跃,孔科,等. 反相高效液相色谱法测定猪血清中的盐酸环丙沙星[J]. 中国兽医科技,2000,30(1) :22-24
[51] Roybal J,Walker CC,Pfenning AP,et al. Concurrent determination of four fluoroquinolones in catfish,shrimp,and salmon by liquid chromatography with fluorescence detection[J]. J AOAC Int,2002,85(6):1293-1301
[52] Johnston L,Mackay L,Croft M. Determination of quinolones and fluoroquinolones in fish tissue and seafood by high-performance liquid chromatography with electrospray ionization tandem mass spectrometric detection[J]. J Chromatogr A,2002,982(1):97-109
[53] Hernandez M,Borrull F,Calull M. Using nonaqueous capillary electrophoresis to analyze several quinolones in pig kidney samples [J]. Electrophoresis,2002,23(3):506-511
[54] A.L. Cinquina, P. Roberti, L.Giannetti, F.Longo, R. Draisci, A. Fagiolo, N.R. Brizioli. Determination of enrofloxacin and its metabolite ciprofloxacinin goat milk by high-performanceliquid chromatography with diode-arraydetection optimization and validation[J]. J. Chromatogr. A, 2003,987: 221-226
[1] F?rster,T. Ann. Phys. 1948,2: 55-75
[2] 陈国珍,黄贤智,许金钩,等. 荧光分析法[M]. 北京:科技出版社,1990:122
[3] Kurokawa, K. Takaya, A. Terai, K.,et al. Acta Histochem. Cytochem [J]. 2004, 37:347
[4] Mathis,G. clin Chem, 1995,41: 1391
[5] 马慧莲,刘含智,王丽萍,等. 量子点的荧光共振能量转移在生物分析中的应用[J]. 分析化学,2005,33(9):1335-1338
[6] 刘春春,杭海英. 生物大分子相互作用检测技术新进展[J]. 生物化学与生物物理进展,2003,3(33):292-296
[7] 章竹君. 能量转移发光分析[J]. 分析试验室,1993,12(1):25-30
[8] 姜永才,吴世康. 在预胶束形成前染料分子的能量转移与预胶束基本性质的研究[J]. 化学学报,1990,43:447-451
[9] 何锡文,唐志新,于贵英,等. 吖啶橙-罗丹明 6G-罗丹明 B 组合成各种混合染料体系的能量转移研究[J]. 分析化学,1994,22(4):332-335
[10] 陈鸿琪,李光源. 吖啶橙(AO)-藏红 T(ST)荧光探针测定 DNA 的研究[J]. 理化检验-化学分册,2000,36(9):385-390
[11] 李小燕,李树伟,曾铭,等. 利用荧光共振能量转移体系测定食品中 NO2—的研究[J]. 分析试验室,2006,25(4):38-41
[12] 李小燕,李树伟,潘建章,等. 荧光共振能量转移体系测定 Cr(Ⅵ)的研究[J]. 四川师范大学学报(自然科学版),2005,28(6):712-714
[13] 刘保生,王桂华,孙汉文,等. 吖啶橙-罗丹明 6G 能量转移荧光法测定痕量磷[J]. 分析化学,2001,29(1):42-44
[14] 刘保生,高静,杨更亮. 吖啶橙-罗丹明 6G 能量转移荧光猝灭法测定维生素 B12[J]. 光谱学与光谱分析,2005,25(7):1080-1082
[15] 林旭聪,谢增鸿,李嘉倩,等. 钙黄绿素-藏红 T 与 DNA 作用机理的光谱研究[J]. 分析测试技术与仪器,2003,9(3):147-151
[16] 宁玲,吕昌银,陈云生,等. PAN-Rh6G 能量转移荧光猝灭法测定水样中痕量镉(II) [J]. 中国卫生检验杂志,2007, 17(8): 1353-1354
[17] Amina Mohamed El-Brashy, Mohamed El-Sayed Metwally, Fawzi Abdallah El-Sepai.Spectrophotometric determination of some fluoroquinolone antibacterials by binary complex formation with xanthene dyes. IL FARMACO 2004; 59: 809–817.
[18] Michael E. El-Kommos, Gamal A. Saleh, Samia M. El-Gizawi, Mohamed,A. Abou-Elwafa. Spectrofluorometric determination of certain quinolones antibacterials using metal chelation. Talanta 2003; 60: 1033-1050.
[19] A. Espinosa-Mansilla, A. Mu?oz de la Pe?a, F. Ca?ada-Ca?ada and D. González Gómez.Determinations of fluoroquinolones and nonsteroidal anti-inflammatory drugs in urine by extractive spectrophotometry and photoinduced spectrofluorimetry using multivariate calibration.Anal. Biochem. 2005; 347: 275-286.
[20] Jianxiu Du, Yinhuan Li, Jiuru Lu. Chemiluminescence determination of fluoroquinolone antibiotics using a soluble manganese (IV)-sulphite system. Luminescence 2005; 20: 30-35.
[21] Hongyan Ma, Xingwang Zheng, Zhujun Zhang. Flow-injection electrogenerated Chemi- luminescence determination of fluoroquinolones based on its sensitizing effect.Luminescence 2005; 20: 303-306.
[22] Katarzyna Michalska, Genowefa Pajchel, Stefan Tyski. Determination of ciprofloxacin and its impurities by capillary zone electrophoresis. J. Chromatogr. A 2004; 1051: 267-272.
[23] Adriana F. Faria, Marcus V.N. de Souza, Mauro V. de Almeida, Marcone A.L. de Oliveira.Simultaneous separation of five fluoroquinolone antibiotics by capillary zone electrophoresis.Anal Chim Acta 2006; 579: 185-192.
[24] E. Vega, V. Dabbene, M. Nassetta and N. Solá. Validation of a reversed-phase LC method for quantitative analysis of intravenous admixtures of ciprofloxacin and metronidazole. J.Pharm. Biomed. Anal. 1999; 21: 1003-1009.
[25] Editorial Committee of the Pharmacopoeia of People’s Republic of China, The Pharmacopoeia of People’s Republic of China (Part II), Chemical Industry Press: Beijing, 2005; pp: 622
[26] Clare Ho, Della W.M. Sin, Hubert P.O. Tang, Lucy P.K. Chung, Sylvia M.P. Siu. Determination and on-line clean-up of ( fluoro ) quinolones in bovine milk using column-switching liquid chromatography fluorescence detection. J. Chromatogr. A 2004; 1061: 123-131.
[27] Marilyn J. Schneider, Susan E. Braden, Ixchel Reyes-Herrera, Dan J. Donoghue.Simult- aneous determination of fluoroquinolones and tetracyclines in chincken muscle using HPLC with fluorescence detection. J. Chromatogr. B 2007; 846: 8-13.
[28] G.H. Wan, H. Cui, Y.L. Pan, P. Zheng, L.J. Liu. Determination of quinolones residues in prawn using high-performance liquid chromatography with Ce(IV)–Ru(bpy)32+–HNO3 chemiluminescence detection. J. Chromatogr. B 2006; 843: 1–9.
[29] A.L. Cinquina, P. Roberti, L.Giannetti, F.Longo, R. Draisci, A. Fagiolo, N.R. Brizioli. Determination of enrofloxacin and its metabolite ciprofloxacinin goat milk by high-performanceliquid chromatography with diode-arraydetection optimization and validation. J. Chromatogr. A 2003; 987: 221-226.
[30] O. Ballesteros, I. Toro, V. Sanz-Nebot, A. Navalón, J.L. Vílchez, J. Barbosa. Determination of fluoroquinolones in human urine by liquid chromatography coupled to pneumatically assisted electrospray ionization mass spectrometry. J. Chromatogr.B 2003; 798: 137–144.
[31] Uwe M. Reinscheid. Direct determination of ciprofloxacin in admixtures with metronidazol and ampicillin by NMR. J. Pharm. Biomed. Anal. 2006; 40: 447-449.
[32] Lakowicz, J.R. Principles of Fluorescence Spectroscopy, seconded. Plenum Press: New York, 1999; Chapter 13.
[33] B. Valeur, J.C. Brochon, New Trends in Fluorescence Spectroscopy, Springer Press: Berlin,2001; 25.
[1] 邢美君,柳兰香.紫外分光光度法测定盐酸环丙沙星的含量[J].黑龙江医药,2002.5(4):247-248
[2] 徐子刚,郑琳,吴清洲.环丙沙星荧光特性的研究[J].药物分析杂志,2003(23):41-43
[3] 中华人民共和国卫生部药典委员会.中国药典(Ⅱ部).北京:化学工业出版社,2005.附录:622
[4] E. Vega, V. Dabbene, M. Nassetta and N. Solá. Journal of Pharmaceutical and Biomedical Analysis, 1999(21): 1003-1009
[5] 李彦威等.季铵盐用于示波极谱测定法测定培氟沙星和环丙沙星[J].分析化学,2002,30(4):454-457
[1] 邵建本,黄星. 氧氟沙星锌和环丙沙星锌的制备及其抑菌实验[J]. 西南国防医药,1998, 334-337
[2] 王丽辉,何汉军. 环丙沙星锌乳膏的制备[J]. 衡阳医学院学报,1997,25(2):200-201
[3] 徐美君,柳兰香. 紫外分光光度法测定盐酸环丙沙星的含量[J]. 黑龙江医药,2002,5 (4):247-248。
[4] 徐子刚,郑琳,吴清洲. 环丙沙星荧光特性的研究[J].药物分析杂志,2003,23(1): 41-43
[5] 中华人民共和国卫生部药典委员会. 中国药典(Ⅱ部). 北京:化学工业出版社,2005. 附录:622。
[6] E.M. Golet,A.C.Alder,A.Hartmann,T.A.Ternes,W.Giger, Anal. Chem. 2001,73: 3632
[7] 李彦威等. 季铵盐用于示波极谱测定法测定培氟沙星和环丙沙星[J]. 分析化学,2002, 30(4):454-457
[8] 杜黎明,晋卫军,董川,等. 喹诺酮类药物的质子化作用和互变构象与光谱分析[J]. 光 谱与光谱学分析,2001,21(4):520
[2] 周国民. 认识抗生素[J]. 中国保健营养,2004,8:22-23
[3] 姬平,呼慧梅. 滥用抗生素的危害[J]. 中国现代医药杂志,2006, 8(7):39
[4] Bayskier A , Chanto t J-F. Classification and structure and activity relationships of fluoroquinolones[J]. Drugs,1995,49 (Suppl2) :16
[5] 范柏. 喹诺酮类抗菌药的作用机制及细菌耐药性的研究进展[J]. 国外医药抗生素分册,2004,25(1):27-29
[6] 张致平. 喹诺酮类抗菌药研究的新进展[J]. 国外医药抗生素分册, 2001,22(6):241-246
[7] 朱秀美, 张志萍, 郭代红,等. 喹诺酮类抗菌药品不良反应分析[J].中华医院感染学杂志,2001,11(4):306-307
[8] 张健, 王虹. 氟喹诺酮类药致28例不良反应及相关因素的临床分析与研究[J]. 中国民康医学杂志,2003,15(5):278-282
[9] 刘明亮,郭惠元,等. 喹诺酮类抗菌药的概况与展望及研究新进展[J]. 国外医药抗生素分册,2001,22(1):1-4
[10] 柴栋,王春. 氟喹诺酮类抗菌药物所致心肌传导紊乱[J].中国药物应用与监测,2005,5:12-15
[11] 蒋天如,屈健. 环丙沙星致急性间质性肾炎1例[J]. 临床误诊误治,1999,12 (3):222-223.
[12] 包军胜. 环丙沙星致急性肾功能衰竭1例[J]. 医药导报,2000,19(1):31
[13] Hadimeri H , Almroth G, Cederbrandt K, et al . Allergic nephrotoxicity associated with norfloxacin and ciprofloxacin therapy[J]. Scand J Urol Nephrol, 1997,31:4812485.
[14] 宋东奎, 王瑞. 氟喹诺酮类药物致肾脏严重不良反应分析[J]. 中华医院感染学杂志,2003,13(4):371-372
[15] Go ldstein FW,A car JF. Epidemiology of quinolone resistance :Europe and no rth and south America. [J]. Drugs, 1995,49 (Supp l2) :36
[16] Turnidge J. Ep idemiology of quinolone resistance :Eastern hemisphere. [J]. D rugs,1995,49 (Supp l2) :43
[17] 医疗情报.システム开发·ソタ 药剂感受性情报. [R ].东京: 药业时报社, 1993
[18] 张致平. 喹诺酮类抗菌药研究的新进展[J]. 国外医药抗生素分册,2001, 22(6):241-283
[19] http://www.ljzy.com.cn/c2045/c2064/w1600.asp
[20] 刘伟祥. 紫外分光光度法测定0.5%环丙沙星滴眼液的含量[J]. 实用医学杂志,1994,10(7):689
[21] 张慧,洪有采,余珲,等. 紫外分光光度法测定盐酸环丙沙星软膏含量[J]. 中国药房,1995,6(4):38
[22] 武洋,张素范,王沪凯,等. 紫外分光光度法测定双唑星栓中乳酸环丙沙星和甲硝唑的含量[J]. 实用药物与临床,2005,8(2):19-21
[23] M Isabel Pascual-Reguera, Gertrudis Pérez Parras, Antonio Molina Díaz. Solid-phase UV spectrophotometric method for determination of ciprofloxacin[J]. Microchemical Journal,2004,77:79-84
[24] 李之琳,陈贵起. 差示分光光度法测定复方环丙沙星滴眼液中环丙沙星含量[J]. 中国药业,2006,15(1):39
[25] 刘瑞玲,徐景仁,刘友皋,等. 盐酸环丙沙星含量的测定方法研究[J]. 药物分析杂志,1994,14(1):45-46
[26] 王妮. 抗菌可溶性止血纱布中环丙沙星的含量测定[J]. 中国新药杂志,2004,13(5):430-431
[27] 高建华,林鹏,刘钺,等. 荧光法测定乳酸环丙沙星的含量 [J]. 河南化工,1999,2:27-28
[28] 徐子刚,郑琳,吴清洲. 环丙沙星荧光特性的研究[J]. 药物分析杂志,2003(23):41-43
[29] 周采菊,卢宁,郭永恩. 荧光光度法测定盐酸环丙沙星软膏的含量[J]. 药物分析杂志,1998,18(3):200-201
[30] 吴淑清,曹秋娥,赵云昆,等. 铽-环丙沙星体系的荧光特性及环丙沙星的测定[J]. 分析化学,2000,28(12):1462-1466
[31] Michael E. El-Kommos, Gamal A. Saleh, Samia M. El-Gizawi等. Spectrofluorometric determination of certain quinolone antibacterials using metal chelation[J]. Talanta,2003(60):1033-1050
[32] 徐瑞云, 刘璇昕, 孙梅佳,等. 环丙沙星和氧氟沙星的荧光光谱法测定[J]. 上海应用技术学院学报,2005,5(1):4-10
[33] 邵爽. 荧光分析法测定滴眼液和片剂中环丙沙星的含量[J]. 浙江教育学院学报,2004,7(4):70-74
[34] 马文诗,刘树春. 高效液相色谱法测定盐酸环丙沙星滴眼液含量的研究[J]. 天津药学,1995,7(4):70-72
[35] 王康俊,蔡珊英,刘汉山. 高效液相色谱法测定盐酸环丙沙星软膏的含量[J]. 药物分析杂志,2001,21(1):43-44
[36] 白林,魏萍,王瑾. 高效液相色谱法测定复方环丙沙星滴鼻液中3组分含量[J]. 解放军药学学报,2002,18(2):79-81
[37] 符成龙,殷栋二,董荣毛. 高效液相色谱法测定盐酸环丙沙星栓的含量[J]. 中国药业,2004,13(11):40
[38] 黄建凡,陈建华,陈奇. 高效液相色谱法测定环丙沙星片剂的尿药浓度[J]. 抗感染药学,2005,2(3):141-142
[39] 陈烨,周云鹏,檀德宏,等. HPLC法同时测定复方盐酸环丙沙星滴耳液两组分的含量[J]. 辽宁大学学报:自然科学版,2006,33(4):327-330
[40] PREDRAG SIBINOVI?,ANDREJA ?MELCEROVI?, RADOSAV PALI?等. Ruggedness testing of an HPLC method for the determination of ciprofloxacin[J]. J. Serb. Chem. Soc,2005,70 (7) :979–986
[41] 汪秀龄,张淑敏,赫春香. 乳酸环丙沙星单扫描示波极谱法研究 [J]. 高等学校化学学报; 1996年06期; 874-877
[42] 李彦威,林建英,魏文珑,等. Gran 电位滴定法测定乳酸环丙沙星[J]. 分析试验室,2005,24(8):79-81
[43] 杜黎明,王静萍,刘艳红. 环丙沙星荷移反应及荧光光谱性质研究[J]. 分析化学,2002, 30(6):658-660
[44] 连宁,王建朝,冷文红,等. 流动注射化学发光法测定环丙沙星[J]. 光谱学与光谱分析,2005,25(7):1038-1041
[45] 宋雅茹,王尚芝. 火焰原子吸收光谱法测定盐酸环丙沙星[J]. 北京师范大学学报:自然科学版,2002,38(1):80-83
[46] 谢志海,袁红安,常斌,等. 间接原子吸收法测定乳酸环丙沙星[J]. 分析试验室,2003 , 22(1 ):78-80
[47] 李红,任乃林. 荧光光度法测定鱼肉中的环丙沙星[J]. 食品科技,2006,9:245-247
[48] 席会平 董学芝 胡卫平,等. 荧光法快速测定鸡血清中环丙沙星的残留量[J].华西药学杂志,2006,21(3):275-277
[49] 席会平 , 董学芝 , 胡卫平,等. 表面活性剂增敏荧光光度法快速测定残留牛奶中的环丙沙星[J]. 中国抗生素杂志,2006,31(5):285-286,313
[50] 伍冶,操继跃,孔科,等. 反相高效液相色谱法测定猪血清中的盐酸环丙沙星[J]. 中国兽医科技,2000,30(1) :22-24
[51] Roybal J,Walker CC,Pfenning AP,et al. Concurrent determination of four fluoroquinolones in catfish,shrimp,and salmon by liquid chromatography with fluorescence detection[J]. J AOAC Int,2002,85(6):1293-1301
[52] Johnston L,Mackay L,Croft M. Determination of quinolones and fluoroquinolones in fish tissue and seafood by high-performance liquid chromatography with electrospray ionization tandem mass spectrometric detection[J]. J Chromatogr A,2002,982(1):97-109
[53] Hernandez M,Borrull F,Calull M. Using nonaqueous capillary electrophoresis to analyze several quinolones in pig kidney samples [J]. Electrophoresis,2002,23(3):506-511
[54] A.L. Cinquina, P. Roberti, L.Giannetti, F.Longo, R. Draisci, A. Fagiolo, N.R. Brizioli. Determination of enrofloxacin and its metabolite ciprofloxacinin goat milk by high-performanceliquid chromatography with diode-arraydetection optimization and validation[J]. J. Chromatogr. A, 2003,987: 221-226
[1] F?rster,T. Ann. Phys. 1948,2: 55-75
[2] 陈国珍,黄贤智,许金钩,等. 荧光分析法[M]. 北京:科技出版社,1990:122
[3] Kurokawa, K. Takaya, A. Terai, K.,et al. Acta Histochem. Cytochem [J]. 2004, 37:347
[4] Mathis,G. clin Chem, 1995,41: 1391
[5] 马慧莲,刘含智,王丽萍,等. 量子点的荧光共振能量转移在生物分析中的应用[J]. 分析化学,2005,33(9):1335-1338
[6] 刘春春,杭海英. 生物大分子相互作用检测技术新进展[J]. 生物化学与生物物理进展,2003,3(33):292-296
[7] 章竹君. 能量转移发光分析[J]. 分析试验室,1993,12(1):25-30
[8] 姜永才,吴世康. 在预胶束形成前染料分子的能量转移与预胶束基本性质的研究[J]. 化学学报,1990,43:447-451
[9] 何锡文,唐志新,于贵英,等. 吖啶橙-罗丹明 6G-罗丹明 B 组合成各种混合染料体系的能量转移研究[J]. 分析化学,1994,22(4):332-335
[10] 陈鸿琪,李光源. 吖啶橙(AO)-藏红 T(ST)荧光探针测定 DNA 的研究[J]. 理化检验-化学分册,2000,36(9):385-390
[11] 李小燕,李树伟,曾铭,等. 利用荧光共振能量转移体系测定食品中 NO2—的研究[J]. 分析试验室,2006,25(4):38-41
[12] 李小燕,李树伟,潘建章,等. 荧光共振能量转移体系测定 Cr(Ⅵ)的研究[J]. 四川师范大学学报(自然科学版),2005,28(6):712-714
[13] 刘保生,王桂华,孙汉文,等. 吖啶橙-罗丹明 6G 能量转移荧光法测定痕量磷[J]. 分析化学,2001,29(1):42-44
[14] 刘保生,高静,杨更亮. 吖啶橙-罗丹明 6G 能量转移荧光猝灭法测定维生素 B12[J]. 光谱学与光谱分析,2005,25(7):1080-1082
[15] 林旭聪,谢增鸿,李嘉倩,等. 钙黄绿素-藏红 T 与 DNA 作用机理的光谱研究[J]. 分析测试技术与仪器,2003,9(3):147-151
[16] 宁玲,吕昌银,陈云生,等. PAN-Rh6G 能量转移荧光猝灭法测定水样中痕量镉(II) [J]. 中国卫生检验杂志,2007, 17(8): 1353-1354
[17] Amina Mohamed El-Brashy, Mohamed El-Sayed Metwally, Fawzi Abdallah El-Sepai.Spectrophotometric determination of some fluoroquinolone antibacterials by binary complex formation with xanthene dyes. IL FARMACO 2004; 59: 809–817.
[18] Michael E. El-Kommos, Gamal A. Saleh, Samia M. El-Gizawi, Mohamed,A. Abou-Elwafa. Spectrofluorometric determination of certain quinolones antibacterials using metal chelation. Talanta 2003; 60: 1033-1050.
[19] A. Espinosa-Mansilla, A. Mu?oz de la Pe?a, F. Ca?ada-Ca?ada and D. González Gómez.Determinations of fluoroquinolones and nonsteroidal anti-inflammatory drugs in urine by extractive spectrophotometry and photoinduced spectrofluorimetry using multivariate calibration.Anal. Biochem. 2005; 347: 275-286.
[20] Jianxiu Du, Yinhuan Li, Jiuru Lu. Chemiluminescence determination of fluoroquinolone antibiotics using a soluble manganese (IV)-sulphite system. Luminescence 2005; 20: 30-35.
[21] Hongyan Ma, Xingwang Zheng, Zhujun Zhang. Flow-injection electrogenerated Chemi- luminescence determination of fluoroquinolones based on its sensitizing effect.Luminescence 2005; 20: 303-306.
[22] Katarzyna Michalska, Genowefa Pajchel, Stefan Tyski. Determination of ciprofloxacin and its impurities by capillary zone electrophoresis. J. Chromatogr. A 2004; 1051: 267-272.
[23] Adriana F. Faria, Marcus V.N. de Souza, Mauro V. de Almeida, Marcone A.L. de Oliveira.Simultaneous separation of five fluoroquinolone antibiotics by capillary zone electrophoresis.Anal Chim Acta 2006; 579: 185-192.
[24] E. Vega, V. Dabbene, M. Nassetta and N. Solá. Validation of a reversed-phase LC method for quantitative analysis of intravenous admixtures of ciprofloxacin and metronidazole. J.Pharm. Biomed. Anal. 1999; 21: 1003-1009.
[25] Editorial Committee of the Pharmacopoeia of People’s Republic of China, The Pharmacopoeia of People’s Republic of China (Part II), Chemical Industry Press: Beijing, 2005; pp: 622
[26] Clare Ho, Della W.M. Sin, Hubert P.O. Tang, Lucy P.K. Chung, Sylvia M.P. Siu. Determination and on-line clean-up of ( fluoro ) quinolones in bovine milk using column-switching liquid chromatography fluorescence detection. J. Chromatogr. A 2004; 1061: 123-131.
[27] Marilyn J. Schneider, Susan E. Braden, Ixchel Reyes-Herrera, Dan J. Donoghue.Simult- aneous determination of fluoroquinolones and tetracyclines in chincken muscle using HPLC with fluorescence detection. J. Chromatogr. B 2007; 846: 8-13.
[28] G.H. Wan, H. Cui, Y.L. Pan, P. Zheng, L.J. Liu. Determination of quinolones residues in prawn using high-performance liquid chromatography with Ce(IV)–Ru(bpy)32+–HNO3 chemiluminescence detection. J. Chromatogr. B 2006; 843: 1–9.
[29] A.L. Cinquina, P. Roberti, L.Giannetti, F.Longo, R. Draisci, A. Fagiolo, N.R. Brizioli. Determination of enrofloxacin and its metabolite ciprofloxacinin goat milk by high-performanceliquid chromatography with diode-arraydetection optimization and validation. J. Chromatogr. A 2003; 987: 221-226.
[30] O. Ballesteros, I. Toro, V. Sanz-Nebot, A. Navalón, J.L. Vílchez, J. Barbosa. Determination of fluoroquinolones in human urine by liquid chromatography coupled to pneumatically assisted electrospray ionization mass spectrometry. J. Chromatogr.B 2003; 798: 137–144.
[31] Uwe M. Reinscheid. Direct determination of ciprofloxacin in admixtures with metronidazol and ampicillin by NMR. J. Pharm. Biomed. Anal. 2006; 40: 447-449.
[32] Lakowicz, J.R. Principles of Fluorescence Spectroscopy, seconded. Plenum Press: New York, 1999; Chapter 13.
[33] B. Valeur, J.C. Brochon, New Trends in Fluorescence Spectroscopy, Springer Press: Berlin,2001; 25.
[1] 邢美君,柳兰香.紫外分光光度法测定盐酸环丙沙星的含量[J].黑龙江医药,2002.5(4):247-248
[2] 徐子刚,郑琳,吴清洲.环丙沙星荧光特性的研究[J].药物分析杂志,2003(23):41-43
[3] 中华人民共和国卫生部药典委员会.中国药典(Ⅱ部).北京:化学工业出版社,2005.附录:622
[4] E. Vega, V. Dabbene, M. Nassetta and N. Solá. Journal of Pharmaceutical and Biomedical Analysis, 1999(21): 1003-1009
[5] 李彦威等.季铵盐用于示波极谱测定法测定培氟沙星和环丙沙星[J].分析化学,2002,30(4):454-457
[1] 邵建本,黄星. 氧氟沙星锌和环丙沙星锌的制备及其抑菌实验[J]. 西南国防医药,1998, 334-337
[2] 王丽辉,何汉军. 环丙沙星锌乳膏的制备[J]. 衡阳医学院学报,1997,25(2):200-201
[3] 徐美君,柳兰香. 紫外分光光度法测定盐酸环丙沙星的含量[J]. 黑龙江医药,2002,5 (4):247-248。
[4] 徐子刚,郑琳,吴清洲. 环丙沙星荧光特性的研究[J].药物分析杂志,2003,23(1): 41-43
[5] 中华人民共和国卫生部药典委员会. 中国药典(Ⅱ部). 北京:化学工业出版社,2005. 附录:622。
[6] E.M. Golet,A.C.Alder,A.Hartmann,T.A.Ternes,W.Giger, Anal. Chem. 2001,73: 3632
[7] 李彦威等. 季铵盐用于示波极谱测定法测定培氟沙星和环丙沙星[J]. 分析化学,2002, 30(4):454-457
[8] 杜黎明,晋卫军,董川,等. 喹诺酮类药物的质子化作用和互变构象与光谱分析[J]. 光 谱与光谱学分析,2001,21(4):520