氟喹诺酮类药物分子印迹溶胶—凝胶吸附剂的制备方法及识别性能研究
|
摘要
利用溶胶-凝胶技术与分子印迹技术相结合的方法,在水相体系中制备氟喹诺酮类药物的分子印迹吸附材料,实现了水相体系中实际样品的选择性分离检测。详细考察了印迹吸附剂的合成条件和识别特性及其主要影响因素,通过Scatchard分析分别计算了其饱和吸附量和离解常数。发展了具有疏水作用、离子对作用的印迹方法和有机/无机互穿网络共聚分子印迹杂化材料的制备方法,并将洛美沙星分子印迹吸附材料用于固相萃取-高效液相色谱法测定牛奶中痕量洛美沙星残留量。全文分为如下四个部分：
第一章：简要介绍了分子印迹技术和溶胶-凝胶技术的基本原理及溶胶-凝胶分子印迹技术在药物分离检测中的研究进展及展望。
第二章：采溶用胶-凝胶法以诺氟沙星为模板,3-氨基丙基三乙氧基硅烷(APS)为功能单体,四乙氧基硅烷(TEOS)为交联剂,添加甲基三甲氧基硅烷(MTMS)增加其疏水性,制备印迹吸附材料。考察了MTMS用量、吸附体系的pH值对聚合物吸附量的影响。通过吸附实验考察聚合物的吸附能力,通过Scatchard分析,计算了聚合物的离解常数和饱和吸附容量,分别为：Kd1=27.2 mg/L (Qmax1=44.48 mg/g)和Kd2=124.1mg/L (Qmax2=46.44mg/g)。
第三章：采用溶胶-凝胶法以洛美沙星为模板,APS为功能单体,MTMS为交联剂,调节反应体系pH值,以功能单体与模板分子的离子对作用方式,合成了印迹聚合物。红外光谱实验和静态吸附实验研究了印迹聚合物的材料性能和吸附特性。将制备的分子印迹聚合物,用于固相萃取柱填料,考察其萃取条件,并用于牛奶中的痕量洛美沙星的富集分离和液相色谱分析,平均回收率为71.1%。
第四章：以甲基丙烯酰氧丙基三甲氧基硅烷与甲基丙烯酸为功能单体,氧氟沙星为印迹模板,四乙氧基硅烷为交联剂,AIBN为引发剂进行了有机-无机共聚合成研究,发展有机/无机互穿网络共聚分子印迹杂化材料的制备方法。研究了合成条件和印迹聚合物的吸附性能。通过Scatchard分析,计算了聚合物的离解常数和饱和吸附容量,分别为：Kd1=51.11mg/L (Qmax1=51.34 mg/g)和Kd2=159.02 mg/L (Qmax2=77.41 mg/g)。
The aim of this dissertation is to develop the molecular imprinting polymers(MIPs) for 6the absorption of fluoroquinolones in the preparation of aqueous system by the combination of sol-gel technique and molecular imprinting technique, which is in order to facilitate selective analysis of the actual samples in the water-phase system. The MIPs recognition properties for the target molecule were investigated by the static adsorption experiments, the maximal adsorption capacity and dissociation constant were calculated by the Scatchard equation. The new imprinting method based on hydrophobic interaction and ion-pairing interaction between the functional monomer and the template molecule were developed, and the synthesis method of organic-inorganic imprinted polymer hybrids having interpenetrating polymer networks structure was investigated. The lomefloxacin-MIPs were used to solid-phase extraction for pre-concentration and determination the lomefloxacin in milk combined with high-performance liquid chromatography technique. The thesis includes four chapters as follows:
Chapter one:A review mainly introduce the principle of sol-gel molecular imprinting technique, the application in drugs, the application in drug of quinolones, as well as the prospect of the sol-gel molecular imprinting technique.
Chapter two:A novel molecularly imprinting polymer was synthesized by combining molecular imprinting technique and sol-gel process with norfloxacin as template, 3-aminopropyltriethoxysilane as functional monomer, and tetraethoxysilane as crosslinker, added methyltrimethoxysilane (MTMS) to increase hydrophobic interaction. The influence of MTMS and the pH of adsorption solution on recognition properties was investigated. The binding capacity was evaluated by static absorption experiment and Scatchard analysis,which showed that the dissociation constant (KD) and the maximum binding capacity(Qmax) were 124.1mg/L and 46.44 mg/g for high affinity binding site, and 27.2 mg/L and 44.48 mg/g for lower affinity binding site respectively.
Chapter three:A molecularly imprinted solid-phase extraction sorbent was synthesized using lomefloxacin as template,3-aminopropyltriethoxysilane as functional monomer, and methyltrimethoxysilane as crosslinker, by sol-gel technique, adjust pH value of the reaction system, use ions pairing action to combine template and functional monomer. The reaction mechanism was reasoned by the infrared spectroscopy analysis, The adsorption capacity of the polymer was evaluated by the static absorption experiment. The lomefloxacin MIPs were used to solid-phase extraction for pre-concentration the rudimental lomefloxacin in milk, the average recovery was 71.1%.
Chapter four:A novel organic-inorganic interpenetrating hybird sorbent was synthesized with ofloxacin as template methacryloxypropyltrimethoxysilane and methacrylic acid as functional monomer and tetraethoxysilane as crosslinker, azobisisbutyronitrile as initiator, the synthesis method of organic-inorganic imprinted polymer hybrids having interpenetrating polymer networks structure was developed. The binding capacity was evaluated by static adsorption experiment and Scatchard analysis,which showed that the dissociation constant(KD) and the maximum binding capacity(Qmax) were 51.11mg/L and 51.34mg/g for high affinity binding site, and 159.02 mg/L and 77.41 mg/g for lower affinity binding site,respectively.
第一章：简要介绍了分子印迹技术和溶胶-凝胶技术的基本原理及溶胶-凝胶分子印迹技术在药物分离检测中的研究进展及展望。
第二章：采溶用胶-凝胶法以诺氟沙星为模板,3-氨基丙基三乙氧基硅烷(APS)为功能单体,四乙氧基硅烷(TEOS)为交联剂,添加甲基三甲氧基硅烷(MTMS)增加其疏水性,制备印迹吸附材料。考察了MTMS用量、吸附体系的pH值对聚合物吸附量的影响。通过吸附实验考察聚合物的吸附能力,通过Scatchard分析,计算了聚合物的离解常数和饱和吸附容量,分别为：Kd1=27.2 mg/L (Qmax1=44.48 mg/g)和Kd2=124.1mg/L (Qmax2=46.44mg/g)。
第三章：采用溶胶-凝胶法以洛美沙星为模板,APS为功能单体,MTMS为交联剂,调节反应体系pH值,以功能单体与模板分子的离子对作用方式,合成了印迹聚合物。红外光谱实验和静态吸附实验研究了印迹聚合物的材料性能和吸附特性。将制备的分子印迹聚合物,用于固相萃取柱填料,考察其萃取条件,并用于牛奶中的痕量洛美沙星的富集分离和液相色谱分析,平均回收率为71.1%。
第四章：以甲基丙烯酰氧丙基三甲氧基硅烷与甲基丙烯酸为功能单体,氧氟沙星为印迹模板,四乙氧基硅烷为交联剂,AIBN为引发剂进行了有机-无机共聚合成研究,发展有机/无机互穿网络共聚分子印迹杂化材料的制备方法。研究了合成条件和印迹聚合物的吸附性能。通过Scatchard分析,计算了聚合物的离解常数和饱和吸附容量,分别为：Kd1=51.11mg/L (Qmax1=51.34 mg/g)和Kd2=159.02 mg/L (Qmax2=77.41 mg/g)。
The aim of this dissertation is to develop the molecular imprinting polymers(MIPs) for 6the absorption of fluoroquinolones in the preparation of aqueous system by the combination of sol-gel technique and molecular imprinting technique, which is in order to facilitate selective analysis of the actual samples in the water-phase system. The MIPs recognition properties for the target molecule were investigated by the static adsorption experiments, the maximal adsorption capacity and dissociation constant were calculated by the Scatchard equation. The new imprinting method based on hydrophobic interaction and ion-pairing interaction between the functional monomer and the template molecule were developed, and the synthesis method of organic-inorganic imprinted polymer hybrids having interpenetrating polymer networks structure was investigated. The lomefloxacin-MIPs were used to solid-phase extraction for pre-concentration and determination the lomefloxacin in milk combined with high-performance liquid chromatography technique. The thesis includes four chapters as follows:
Chapter one:A review mainly introduce the principle of sol-gel molecular imprinting technique, the application in drugs, the application in drug of quinolones, as well as the prospect of the sol-gel molecular imprinting technique.
Chapter two:A novel molecularly imprinting polymer was synthesized by combining molecular imprinting technique and sol-gel process with norfloxacin as template, 3-aminopropyltriethoxysilane as functional monomer, and tetraethoxysilane as crosslinker, added methyltrimethoxysilane (MTMS) to increase hydrophobic interaction. The influence of MTMS and the pH of adsorption solution on recognition properties was investigated. The binding capacity was evaluated by static absorption experiment and Scatchard analysis,which showed that the dissociation constant (KD) and the maximum binding capacity(Qmax) were 124.1mg/L and 46.44 mg/g for high affinity binding site, and 27.2 mg/L and 44.48 mg/g for lower affinity binding site respectively.
Chapter three:A molecularly imprinted solid-phase extraction sorbent was synthesized using lomefloxacin as template,3-aminopropyltriethoxysilane as functional monomer, and methyltrimethoxysilane as crosslinker, by sol-gel technique, adjust pH value of the reaction system, use ions pairing action to combine template and functional monomer. The reaction mechanism was reasoned by the infrared spectroscopy analysis, The adsorption capacity of the polymer was evaluated by the static absorption experiment. The lomefloxacin MIPs were used to solid-phase extraction for pre-concentration the rudimental lomefloxacin in milk, the average recovery was 71.1%.
Chapter four:A novel organic-inorganic interpenetrating hybird sorbent was synthesized with ofloxacin as template methacryloxypropyltrimethoxysilane and methacrylic acid as functional monomer and tetraethoxysilane as crosslinker, azobisisbutyronitrile as initiator, the synthesis method of organic-inorganic imprinted polymer hybrids having interpenetrating polymer networks structure was developed. The binding capacity was evaluated by static adsorption experiment and Scatchard analysis,which showed that the dissociation constant(KD) and the maximum binding capacity(Qmax) were 51.11mg/L and 51.34mg/g for high affinity binding site, and 159.02 mg/L and 77.41 mg/g for lower affinity binding site,respectively.
引文
[1]Pauling L.. A theory of the structure and process of formation of antibodies. J. Am. Chem.Soc.,1940, 62:2643-2657.
[2]Dichey F. H.. The Preparation of Specific Adsorbents. Natl. Acad. Sci.,1949,35:277-299.
[3]Wulff G., Sarhan A.. Use of polymers with enzyme analogues structures for the resolution of racemates. Angew Chem. Int. Ed. Engl.,1972,11:341.
[4]Wulff G, Sahan A., Zabrocki K.. Enzyme Analogue Built Polymers and Their Use for the Resolution of Racements. Tetrahedron Lett.,1973,14:4329-4332.
[5]Vlatakis G., Andersson L. I., Muller R., Mosbach K.. Drug Assay Using Antibody Mimics Made by Molecular Impringting. Nature,1993,361:645-647.
[6]吕运开,严秀平.分子印迹溶胶·凝胶材料的制备及应用,分析化学,2005,2,(2)：254-260.
[7]Dai S., Shin Y. S., Barnes C. E., Toth L. M.. Enhancement of uranyl adsorption capacity and selectivity on silica sol-gel glasses via molecular imprinting. Chem. Mater.,1997,9:2521-2525.
[8]Jiang X. M., Tian W., Zhao C. D., Zhang H. X., Liu M. C. A novel sol-gel-material prepared by a surface imprinting technique for the selective solid-phase extraction of bisphenol A. Talanta,2007, (72):119-125.
[9]Xu Z. X., Chen S., Huang W., Fang G. Z., Hua P. Z., Wang S.. Study on an on-line molecularly imprinted solid-phase extraction coupled to high-performance liquid chromatography for separation and determination of trace estrone in environment. Anal. Bioanal. Chem.,2009,393:1273-1279.
[10]He J. X., Wang S., Fang G. Z., Zhu H. P., Zhang Y.. Molecularly Imprinted Polymer Online Solid-Phase Extraction Coupled with High-Performance Liquid Chromatography-UV for the Determination of Three Sulfonamides in Pork and Chicken. J. Agric. Food. Chem.,2008,56, 2919-2925.
[11]Wang S., Xu Z., Fang G., Zhang Y., He J. Separation and determination of estrone in environmental and drinking water using molecularly imprinted solid phase extraction coupled with HPLC. J. Sep. Sci.,2008,31 (6-7):1181-1188.
[12]Jiang X. M., Zhao C. D., Jiang N., Zhang H. X., Liu M. C.. Selective solid-phase extraction using molecular imprinted polymer for the analysis of diethylstilbestrol. Food Chem.,2008,108(3): 1061-1067.
[13]He C., Long Y., Pan J., Li K., Liu F.. Molecularly imprinted silica prepared with immiscible ionic liquid as solvent and porogen for selective recognition of testosterone. Talanta,2008,74 (5): 1126-1131.
[14]Fernandez-Gonzalez A., Badia Lai no R., Diaz-Garcia M. E., Guardia L., Viale A.. Assessment of molecularly imprinted sol-gel materials for selective room temperature phosphorescence recognition of nafcillin. J. Chromatogr. B.,2004,804,247-254.
[15]Guardia L., Badiaa R., Marta E. Diaaz-Garciaa. Molecularly Imprinted Sol-Gels for Nafcillin Determination in Milk-Based Products. J. Agric. Food. Chem.2007,55,566-570.
[16]Guardia L., Badia R., Diaz-Garcia, Ania C. O., Parra J. B.. Role of surface adsorption and porosity features in the molecular recognition ability of imprinted sol-gels. Biosens. Bioelectron.,2008,23 (7): 1101-1108.
[17]Han D. M., Fang G. Z., Yan X. P.. Preparation and evaluation of a molecularly imprinted sol-gel material for on-line solid-phase extraction coupled with high performance liquid chromatography for the determination of trace pentachlorophenol in water samples. J. Chromatogr. A.,2005, (1100): 131-136.
[18]Zhang X. L., Dieter Martens, Petra M. Kr"amer,Antonius A. Kettrup, Liang X. M.. Development and application of a sol-gel immunosorbent-based method for the determination of isoproturon in surface water. J. Chromatogr. A.,2006, (1102):84-90.
[19]Jin G. Y., Tang Y. W.. Evaluation of a novel silica-supported sol-gel sorbent prepared by a surface molecular imprinting technique for the selective separation of estazolam from human plasma. Microchim Acta,2009,165:143-149.
[20]Mitch K.-P. Leung, Cheuk-Fai Chow, Michael H.-W. Lam. A sol-gel derived molecular imprinted luminescent PET sensing material for 2,4-dichlorophenoxyacetic acid. J. Mater. Chem.,2001,11, 2985-2991.
[21]Farrington K., Regan F.. Molecularly imprinted sol gel for ibuprofen:An analytical study of the factors influencing selectivity. Talanta,2009, (78):653-659.
[22]Raquel Gomes da Costa Silva, Fabio Augusto. Sol-gel molecular imprinted ormosil for solid-phase extraction of methylxanthines. J. Chromatogr. A.,2006,1114:216-223.
[23]Aisling Olwill, Helen Hughes, Mich'ael O'Riordain, Peter McLoughlin. The use of molecularly imprinted sol-gels in pharmaceutical separations. Biosens. Bioelectron.,2004, (20):1045-1050.
[24]Zhang Y. Q., Zhang Y. H., Qin Z., Ma Z. R.. Synthesis of silica adsorbent and its selective separation for flavone. Front. Chem. China,2008,3 (3):320-324.
[25]冯忠武.兽药与动物性食品安全.中国兽药杂志,2004,38：1-5.
[26]杨玉社,赵善荣,嵇汝运,陈凯先.喹诺酮化合物研究最新进展—抗肿瘤喹诺酮.药学学报,1998,33(2)：157-159.
[27]郭洪声,何锡文,周杰,梁宏.药物氟哌酸分子模板聚合物的分子识别特性.分析化学,2001,29(2)：128-132.
[28]卢春阳,马向霞,何锡文,李文友,陈朗星,何海成.药物氟哌酸分子印迹聚合物膜的制备及其渗透性质研究.高等学校化学学报,2005,26(7)：1356-1359.
[29]孔俊,韩德满,林晓雯.氟哌酸分子印迹溶胶-凝胶材料的制备及评价.科学技术与工程,2008,8(12)：3124-3126.
[30]孙慧,董襄朝,吕宪禹,王海波,韩建仿.以分子印迹聚合物为固定相分离和测定氟喹诺酮类 药物.色谱,2003,21(3)：233-238.
[31]邴乃慈,许振良,杨座国,王学军,冯建立.热聚合制备左氧氟沙星分子印迹聚合物的分子识别特.应用化学,2006,23(10)：1085-1089.
[32]邴乃慈,许振良,杨座国,王学军.热聚合制备左旋氧氟沙星分子印迹聚合物的条件.南京工业大学学报,2006,28(1)：41-45.
[33]邴乃慈,许振良,王学军,杨座国.左氧氟沙星分子印迹膜固相萃取选择性分离氧氟沙星.华东理工大学学报(自然科学版),2007,33(2)：163-166.
[34]曹玺珉,廖玲,杜黎明.依诺沙星分子印迹聚合物的分子识别.应用化学,2008,25(1)：43-47.
[35]张毅,董襄朝.活性/可控自由基聚合制备恩诺沙星印迹微球及识别性能研究.分析测试学报,2008,27(10)：1025-1030.
[36]Sun H. W., Qiao F. W.. Recognition mechanism of water-compatible molecularly imprinted solid-phase extraction and determination of nine quinolones in urine by high performance liquid chromatography. J. Chromatogr. A.,2008,1212(1-2):1-9.
[37]孔俊,韩德满,林晓雯.氟哌酸分子印迹溶胶-凝胶材料的制备及评价.科学技术与工程,2008,18(12)：3124-3126.
[38]Yan H. Y., Qiao F. X., Row K. H.. Molecularly Imprinted-Matrix Solid-Phase Dispersion for Selective Extraction of Five Fluoroquinolones in Eggs and Tissue. Anal. Chem.,2007,79 (21), 8242-8248.
[39]Yan H. Y., Row K. H., Yang G. L.. Water-compatible molecularly imprinted polymers for selective extraction of ciprofloxacin from human urine. Talanta,2008, (75):227-232.
[40]Yan H. Y., Tian M. L., Row K. H.. Determination of enrofloxacin and ciprofloxacin in milk using molecularly imprinted solid-phase extraction. J. Sep. Sci.,2008,31,3015-3020.
[41]Caro E., Rosa M. Marce, Peter A. G. Cormack, David C. Sherrington, Borrull F.. Novel enrofloxacin imprinted polymer applied to the solid-phase extraction of fluorinated quinolones from urine and tissue samples. Anal. Chim. Acta,2006,562:145-151.
[42]Carlucci G. Analysis of fluoroquinolones in biological fluids by high-performance liquid chromatography. J. Chromatogr. A.,1998,812:343-367.
[43]J.A. Hernandez-Arteseros, J. Barbosa, R. Compano, M.D. Prat. Analysis of quinolone residues in edible animal products. J. Chromatogr. A.,2002,945:1-24.
[44]Molinelli A., Weiss R., Mizaikoff B.. Advanced Solid Phase Extraction Using Molecularly Imprinted Polymers for the Determination of Quercetin in Red Wine. J. Agric. Food. Chem.,2002,50(7): 1804-1808.
[45]Lin C. I., Joseph A. K., Chang C. K., Wang Y. C., Lee Y. D.. Synthesis of molecular imprinted organic-inorganic hybrid polymer binding caffeine. Anal. Chim. Acta,2003,481(1):175-180.
[46]Zhu X. L., Yang J., Su Q. D., Cai J.B., Gao Y.. Selective solid-phase extraction using molecularly imprinted polymer for the analysis of polar organophosphorus pesticides in water and soil samples. J. Chromatogr. A.,2005,1092:161-169.
[47]赖家平,何锡文,郭洪声,梁宏.分子印迹技术的回顾、现状与展望.分析化学,2001,29(7)：836-844.
[48]Lu Y. K., Zhao N., Qin X. Y., Liu Y., Lu G. D.. Preparation and application of the sacrificial mesoporous silica imprinted polymers for the selective solid-phase extraction of ofloxacin residues in chicken. Chem. J. Int.,2008,10(6):32.
[49]杜小燕,彭涛,李俊锁.沙拉沙星分子印迹聚合物的制备及其吸附特性.分析化学,2003,31(6)：720-722.
[50]杜黎明,曹玺珉,陈彩萍,段亚丽.左旋氧氟沙星分子模板聚合物的分子识别.分析化学,2004,32(10)：1419.
[51]Turiel E., Marti n-Esteban A., Tadeo J. L.. Molecular imprinting-based separation methods for selective analysis of fluoroquinolones in soils. J. Chromatogr. A.,2007,1172:97-104.
[52]Alvarez-Lorenzo C., Yanez F., Barreiro-Iglesias R., Concheiro A.. Imprinted soft contact lenses as norfloxacin delivery systems. J. Controlled Release,2006,113:236-244.
[53]He Y. H.,Lu J. R.,Zhang H. G..Du J. X.. Molecular Imprinting-Chemiluminescence Determination of Norfloxacin Using a Norfloxacin-Imprinted Polymer as the Recognition Material. Microchim Acta, 2005,149:239-244.
[54]Andrew G.. Mayes, Mosbach K.. Molecularly Imprinted Polymer Beads:Suspension Polymerization Using a Liquid Perfluorocarbon as the Dispersing Phase. Anal. Chem.,1996,68:3769-3774.
[55]Zhou J., He X. W., Li Y. J.. Binding study on 5,5-diphenylhydantoin imprinted polymer constructed by utilizing an amide functional group. Anal. Chim. Acta,1999,394:353-359.
[56]连宁,唐江宏,贺香红,李卫华,周全法.能量转移化学发光法测定洛美沙星.分析化学,2008,36(6)：823-826.
[57]Garcia M. A., Solans C., Calvo A., Hernandez E., Rey R., Bregante M. A., Puig M.. Determination of enrofloxacin and its primary metabolite,ciprofloxacin, in pig tissues. Application to residue studies. Biomed. Chromatogr.2005(19):27-31.
[58]刘晓红,王殿夫.鲤鱼中恩诺/环丙沙星残留量的酶联免疫检测.食品科学,2008,29(09)：491-493.
[59]Marazuela M.D., Moreno-Bondi M.C.. Multiresidue determination of fluoroquinolones in milk by column liquid chromatography with fluorescence and ultraviolet absorbance detection. J. Chromatogr A,2004, (1034):25-32.
[60]Idowu O. R.,. Peggins J. O.. Simple, rapid determination of enrofloxacin and ciprofloxacin in bovine milk and plasma by high-performance liquid chromatography with fluorescence detection. Journal of Pharmaceutical and Biomedical Analysis 2004, (35):143-153.
[61]Andersson L. I.. Molecular imprinting:developments and applications in the analytical chemistry field. J. Chromatogr. B.,2000,745(1):3-13.
[62]Lei J. D.,Tan T. M.. Chiral separation of naproxen on molecular imprinted polymers. mod. chem. industry,2001,21(8):29-33.
[63]李萍,胡溶哲,林保平.以混旋邻氯扁桃酸为模板的分子印迹聚合物的制备及拆分性能研究.化学学报,2003,61(11)：1885-1889.
[64]赖家平,卢春阳,何锡文.水溶液悬浮聚合法制备酸药物吲哚美辛分子印迹微球及其色谱表征.高等学校化学学报,2003,24(7)：1175-1179.
[65]Martin P., Wilson I. D., Morgan D. E.. Evaluation of a molecular imprinted polymer for use in the solid-phase extraction of propranolol from biological flulds. Anal Commun.,1997,34(6):45-51.
[66]卢春阳,何海成,马向霞.除草剂青莠定分子印迹聚合物的合成及结合性能研究.化学学报,2004,62(8)：799-803.
[67]王宁,董襄朝,张学炜.单嘧磺隆除草剂分子印迹聚合物的识别特性研究.分析测试学报,2004,23(4)：13-17.
[68]Masque N., Marce R. M., BormL F.. Synthesis and evaluation of a molecularly imprinted polymer for selective on-line solid-phase extraction of 4-nitrophenol from environmental water. Anal. Chim. Acta,2001,432(2):227-282.
[69]陆书来,成国祥,蔡志江.蛋白质模板印迹法制备纳米“孔穴”结构特异性生物材料.中国医学科学院学报,2003,25(5)：640-644.
[70]朱庆枝,李顺华.仿生荧光免疫分析卵清白蛋白.福州大学学报,1999,27(9)：116-117.
[71]Lee K., Itharaju R. R., Puleo D. A.. Protein-imprinted polysiloxane scaffolds. Acta Biomater.,2007, 3:515-522.
[72]Bhim B. P., Shouri B.. Preparation,characterization and performance of a silica gel bonded molecularly imprinted polymer for selective recognition and enrichment of β-lactam antibiotics. Reactive & Functional Polymers,2003,55(11):159-169.
[73]Sellergren B.. Direct drug determination by selective enrichment on an imprinted polymer. Anal.Chem.1994,66:1578-1582.
[74]Zurutuza A., Bayoudh S., Cormack P. A. G., Dambies L., Deere J., Bischoff R., Sherrington D. C.. Molecularly imprinted solid-phase extraction of cocaine metabolites from aqueous samples. Anal. Chim. Acta,2005, (542):14-19.
[75]De Prada A. G. V., Martinez-Ruiz P., Reviejo A. J., Pingarron J. M.. Solid-phase molecularly imprinted on-line preconcentration and voltammetric determination of sulfamethazine in milk. Anal. Chim Acta,2005,539:125-132.
[76]Makote R., Maryanne M.. Template Recognition in Inorganic-Organic Hybrid Films Prepared by the Sol-Gel Process. Collinson. Chem. Mater.,1998,10:2440-2445.
[77]Jin, G., Tang, Y., Liu, S., Wang, S., Xing R.. Preparation and application of a novel silica-supported organic-inorganic hybrid molecular imprinting polymer. Anal. Lett.,2008,41 (10):1811-1817.
[2]Dichey F. H.. The Preparation of Specific Adsorbents. Natl. Acad. Sci.,1949,35:277-299.
[3]Wulff G., Sarhan A.. Use of polymers with enzyme analogues structures for the resolution of racemates. Angew Chem. Int. Ed. Engl.,1972,11:341.
[4]Wulff G, Sahan A., Zabrocki K.. Enzyme Analogue Built Polymers and Their Use for the Resolution of Racements. Tetrahedron Lett.,1973,14:4329-4332.
[5]Vlatakis G., Andersson L. I., Muller R., Mosbach K.. Drug Assay Using Antibody Mimics Made by Molecular Impringting. Nature,1993,361:645-647.
[6]吕运开,严秀平.分子印迹溶胶·凝胶材料的制备及应用,分析化学,2005,2,(2)：254-260.
[7]Dai S., Shin Y. S., Barnes C. E., Toth L. M.. Enhancement of uranyl adsorption capacity and selectivity on silica sol-gel glasses via molecular imprinting. Chem. Mater.,1997,9:2521-2525.
[8]Jiang X. M., Tian W., Zhao C. D., Zhang H. X., Liu M. C. A novel sol-gel-material prepared by a surface imprinting technique for the selective solid-phase extraction of bisphenol A. Talanta,2007, (72):119-125.
[9]Xu Z. X., Chen S., Huang W., Fang G. Z., Hua P. Z., Wang S.. Study on an on-line molecularly imprinted solid-phase extraction coupled to high-performance liquid chromatography for separation and determination of trace estrone in environment. Anal. Bioanal. Chem.,2009,393:1273-1279.
[10]He J. X., Wang S., Fang G. Z., Zhu H. P., Zhang Y.. Molecularly Imprinted Polymer Online Solid-Phase Extraction Coupled with High-Performance Liquid Chromatography-UV for the Determination of Three Sulfonamides in Pork and Chicken. J. Agric. Food. Chem.,2008,56, 2919-2925.
[11]Wang S., Xu Z., Fang G., Zhang Y., He J. Separation and determination of estrone in environmental and drinking water using molecularly imprinted solid phase extraction coupled with HPLC. J. Sep. Sci.,2008,31 (6-7):1181-1188.
[12]Jiang X. M., Zhao C. D., Jiang N., Zhang H. X., Liu M. C.. Selective solid-phase extraction using molecular imprinted polymer for the analysis of diethylstilbestrol. Food Chem.,2008,108(3): 1061-1067.
[13]He C., Long Y., Pan J., Li K., Liu F.. Molecularly imprinted silica prepared with immiscible ionic liquid as solvent and porogen for selective recognition of testosterone. Talanta,2008,74 (5): 1126-1131.
[14]Fernandez-Gonzalez A., Badia Lai no R., Diaz-Garcia M. E., Guardia L., Viale A.. Assessment of molecularly imprinted sol-gel materials for selective room temperature phosphorescence recognition of nafcillin. J. Chromatogr. B.,2004,804,247-254.
[15]Guardia L., Badiaa R., Marta E. Diaaz-Garciaa. Molecularly Imprinted Sol-Gels for Nafcillin Determination in Milk-Based Products. J. Agric. Food. Chem.2007,55,566-570.
[16]Guardia L., Badia R., Diaz-Garcia, Ania C. O., Parra J. B.. Role of surface adsorption and porosity features in the molecular recognition ability of imprinted sol-gels. Biosens. Bioelectron.,2008,23 (7): 1101-1108.
[17]Han D. M., Fang G. Z., Yan X. P.. Preparation and evaluation of a molecularly imprinted sol-gel material for on-line solid-phase extraction coupled with high performance liquid chromatography for the determination of trace pentachlorophenol in water samples. J. Chromatogr. A.,2005, (1100): 131-136.
[18]Zhang X. L., Dieter Martens, Petra M. Kr"amer,Antonius A. Kettrup, Liang X. M.. Development and application of a sol-gel immunosorbent-based method for the determination of isoproturon in surface water. J. Chromatogr. A.,2006, (1102):84-90.
[19]Jin G. Y., Tang Y. W.. Evaluation of a novel silica-supported sol-gel sorbent prepared by a surface molecular imprinting technique for the selective separation of estazolam from human plasma. Microchim Acta,2009,165:143-149.
[20]Mitch K.-P. Leung, Cheuk-Fai Chow, Michael H.-W. Lam. A sol-gel derived molecular imprinted luminescent PET sensing material for 2,4-dichlorophenoxyacetic acid. J. Mater. Chem.,2001,11, 2985-2991.
[21]Farrington K., Regan F.. Molecularly imprinted sol gel for ibuprofen:An analytical study of the factors influencing selectivity. Talanta,2009, (78):653-659.
[22]Raquel Gomes da Costa Silva, Fabio Augusto. Sol-gel molecular imprinted ormosil for solid-phase extraction of methylxanthines. J. Chromatogr. A.,2006,1114:216-223.
[23]Aisling Olwill, Helen Hughes, Mich'ael O'Riordain, Peter McLoughlin. The use of molecularly imprinted sol-gels in pharmaceutical separations. Biosens. Bioelectron.,2004, (20):1045-1050.
[24]Zhang Y. Q., Zhang Y. H., Qin Z., Ma Z. R.. Synthesis of silica adsorbent and its selective separation for flavone. Front. Chem. China,2008,3 (3):320-324.
[25]冯忠武.兽药与动物性食品安全.中国兽药杂志,2004,38：1-5.
[26]杨玉社,赵善荣,嵇汝运,陈凯先.喹诺酮化合物研究最新进展—抗肿瘤喹诺酮.药学学报,1998,33(2)：157-159.
[27]郭洪声,何锡文,周杰,梁宏.药物氟哌酸分子模板聚合物的分子识别特性.分析化学,2001,29(2)：128-132.
[28]卢春阳,马向霞,何锡文,李文友,陈朗星,何海成.药物氟哌酸分子印迹聚合物膜的制备及其渗透性质研究.高等学校化学学报,2005,26(7)：1356-1359.
[29]孔俊,韩德满,林晓雯.氟哌酸分子印迹溶胶-凝胶材料的制备及评价.科学技术与工程,2008,8(12)：3124-3126.
[30]孙慧,董襄朝,吕宪禹,王海波,韩建仿.以分子印迹聚合物为固定相分离和测定氟喹诺酮类 药物.色谱,2003,21(3)：233-238.
[31]邴乃慈,许振良,杨座国,王学军,冯建立.热聚合制备左氧氟沙星分子印迹聚合物的分子识别特.应用化学,2006,23(10)：1085-1089.
[32]邴乃慈,许振良,杨座国,王学军.热聚合制备左旋氧氟沙星分子印迹聚合物的条件.南京工业大学学报,2006,28(1)：41-45.
[33]邴乃慈,许振良,王学军,杨座国.左氧氟沙星分子印迹膜固相萃取选择性分离氧氟沙星.华东理工大学学报(自然科学版),2007,33(2)：163-166.
[34]曹玺珉,廖玲,杜黎明.依诺沙星分子印迹聚合物的分子识别.应用化学,2008,25(1)：43-47.
[35]张毅,董襄朝.活性/可控自由基聚合制备恩诺沙星印迹微球及识别性能研究.分析测试学报,2008,27(10)：1025-1030.
[36]Sun H. W., Qiao F. W.. Recognition mechanism of water-compatible molecularly imprinted solid-phase extraction and determination of nine quinolones in urine by high performance liquid chromatography. J. Chromatogr. A.,2008,1212(1-2):1-9.
[37]孔俊,韩德满,林晓雯.氟哌酸分子印迹溶胶-凝胶材料的制备及评价.科学技术与工程,2008,18(12)：3124-3126.
[38]Yan H. Y., Qiao F. X., Row K. H.. Molecularly Imprinted-Matrix Solid-Phase Dispersion for Selective Extraction of Five Fluoroquinolones in Eggs and Tissue. Anal. Chem.,2007,79 (21), 8242-8248.
[39]Yan H. Y., Row K. H., Yang G. L.. Water-compatible molecularly imprinted polymers for selective extraction of ciprofloxacin from human urine. Talanta,2008, (75):227-232.
[40]Yan H. Y., Tian M. L., Row K. H.. Determination of enrofloxacin and ciprofloxacin in milk using molecularly imprinted solid-phase extraction. J. Sep. Sci.,2008,31,3015-3020.
[41]Caro E., Rosa M. Marce, Peter A. G. Cormack, David C. Sherrington, Borrull F.. Novel enrofloxacin imprinted polymer applied to the solid-phase extraction of fluorinated quinolones from urine and tissue samples. Anal. Chim. Acta,2006,562:145-151.
[42]Carlucci G. Analysis of fluoroquinolones in biological fluids by high-performance liquid chromatography. J. Chromatogr. A.,1998,812:343-367.
[43]J.A. Hernandez-Arteseros, J. Barbosa, R. Compano, M.D. Prat. Analysis of quinolone residues in edible animal products. J. Chromatogr. A.,2002,945:1-24.
[44]Molinelli A., Weiss R., Mizaikoff B.. Advanced Solid Phase Extraction Using Molecularly Imprinted Polymers for the Determination of Quercetin in Red Wine. J. Agric. Food. Chem.,2002,50(7): 1804-1808.
[45]Lin C. I., Joseph A. K., Chang C. K., Wang Y. C., Lee Y. D.. Synthesis of molecular imprinted organic-inorganic hybrid polymer binding caffeine. Anal. Chim. Acta,2003,481(1):175-180.
[46]Zhu X. L., Yang J., Su Q. D., Cai J.B., Gao Y.. Selective solid-phase extraction using molecularly imprinted polymer for the analysis of polar organophosphorus pesticides in water and soil samples. J. Chromatogr. A.,2005,1092:161-169.
[47]赖家平,何锡文,郭洪声,梁宏.分子印迹技术的回顾、现状与展望.分析化学,2001,29(7)：836-844.
[48]Lu Y. K., Zhao N., Qin X. Y., Liu Y., Lu G. D.. Preparation and application of the sacrificial mesoporous silica imprinted polymers for the selective solid-phase extraction of ofloxacin residues in chicken. Chem. J. Int.,2008,10(6):32.
[49]杜小燕,彭涛,李俊锁.沙拉沙星分子印迹聚合物的制备及其吸附特性.分析化学,2003,31(6)：720-722.
[50]杜黎明,曹玺珉,陈彩萍,段亚丽.左旋氧氟沙星分子模板聚合物的分子识别.分析化学,2004,32(10)：1419.
[51]Turiel E., Marti n-Esteban A., Tadeo J. L.. Molecular imprinting-based separation methods for selective analysis of fluoroquinolones in soils. J. Chromatogr. A.,2007,1172:97-104.
[52]Alvarez-Lorenzo C., Yanez F., Barreiro-Iglesias R., Concheiro A.. Imprinted soft contact lenses as norfloxacin delivery systems. J. Controlled Release,2006,113:236-244.
[53]He Y. H.,Lu J. R.,Zhang H. G..Du J. X.. Molecular Imprinting-Chemiluminescence Determination of Norfloxacin Using a Norfloxacin-Imprinted Polymer as the Recognition Material. Microchim Acta, 2005,149:239-244.
[54]Andrew G.. Mayes, Mosbach K.. Molecularly Imprinted Polymer Beads:Suspension Polymerization Using a Liquid Perfluorocarbon as the Dispersing Phase. Anal. Chem.,1996,68:3769-3774.
[55]Zhou J., He X. W., Li Y. J.. Binding study on 5,5-diphenylhydantoin imprinted polymer constructed by utilizing an amide functional group. Anal. Chim. Acta,1999,394:353-359.
[56]连宁,唐江宏,贺香红,李卫华,周全法.能量转移化学发光法测定洛美沙星.分析化学,2008,36(6)：823-826.
[57]Garcia M. A., Solans C., Calvo A., Hernandez E., Rey R., Bregante M. A., Puig M.. Determination of enrofloxacin and its primary metabolite,ciprofloxacin, in pig tissues. Application to residue studies. Biomed. Chromatogr.2005(19):27-31.
[58]刘晓红,王殿夫.鲤鱼中恩诺/环丙沙星残留量的酶联免疫检测.食品科学,2008,29(09)：491-493.
[59]Marazuela M.D., Moreno-Bondi M.C.. Multiresidue determination of fluoroquinolones in milk by column liquid chromatography with fluorescence and ultraviolet absorbance detection. J. Chromatogr A,2004, (1034):25-32.
[60]Idowu O. R.,. Peggins J. O.. Simple, rapid determination of enrofloxacin and ciprofloxacin in bovine milk and plasma by high-performance liquid chromatography with fluorescence detection. Journal of Pharmaceutical and Biomedical Analysis 2004, (35):143-153.
[61]Andersson L. I.. Molecular imprinting:developments and applications in the analytical chemistry field. J. Chromatogr. B.,2000,745(1):3-13.
[62]Lei J. D.,Tan T. M.. Chiral separation of naproxen on molecular imprinted polymers. mod. chem. industry,2001,21(8):29-33.
[63]李萍,胡溶哲,林保平.以混旋邻氯扁桃酸为模板的分子印迹聚合物的制备及拆分性能研究.化学学报,2003,61(11)：1885-1889.
[64]赖家平,卢春阳,何锡文.水溶液悬浮聚合法制备酸药物吲哚美辛分子印迹微球及其色谱表征.高等学校化学学报,2003,24(7)：1175-1179.
[65]Martin P., Wilson I. D., Morgan D. E.. Evaluation of a molecular imprinted polymer for use in the solid-phase extraction of propranolol from biological flulds. Anal Commun.,1997,34(6):45-51.
[66]卢春阳,何海成,马向霞.除草剂青莠定分子印迹聚合物的合成及结合性能研究.化学学报,2004,62(8)：799-803.
[67]王宁,董襄朝,张学炜.单嘧磺隆除草剂分子印迹聚合物的识别特性研究.分析测试学报,2004,23(4)：13-17.
[68]Masque N., Marce R. M., BormL F.. Synthesis and evaluation of a molecularly imprinted polymer for selective on-line solid-phase extraction of 4-nitrophenol from environmental water. Anal. Chim. Acta,2001,432(2):227-282.
[69]陆书来,成国祥,蔡志江.蛋白质模板印迹法制备纳米“孔穴”结构特异性生物材料.中国医学科学院学报,2003,25(5)：640-644.
[70]朱庆枝,李顺华.仿生荧光免疫分析卵清白蛋白.福州大学学报,1999,27(9)：116-117.
[71]Lee K., Itharaju R. R., Puleo D. A.. Protein-imprinted polysiloxane scaffolds. Acta Biomater.,2007, 3:515-522.
[72]Bhim B. P., Shouri B.. Preparation,characterization and performance of a silica gel bonded molecularly imprinted polymer for selective recognition and enrichment of β-lactam antibiotics. Reactive & Functional Polymers,2003,55(11):159-169.
[73]Sellergren B.. Direct drug determination by selective enrichment on an imprinted polymer. Anal.Chem.1994,66:1578-1582.
[74]Zurutuza A., Bayoudh S., Cormack P. A. G., Dambies L., Deere J., Bischoff R., Sherrington D. C.. Molecularly imprinted solid-phase extraction of cocaine metabolites from aqueous samples. Anal. Chim. Acta,2005, (542):14-19.
[75]De Prada A. G. V., Martinez-Ruiz P., Reviejo A. J., Pingarron J. M.. Solid-phase molecularly imprinted on-line preconcentration and voltammetric determination of sulfamethazine in milk. Anal. Chim Acta,2005,539:125-132.
[76]Makote R., Maryanne M.. Template Recognition in Inorganic-Organic Hybrid Films Prepared by the Sol-Gel Process. Collinson. Chem. Mater.,1998,10:2440-2445.
[77]Jin, G., Tang, Y., Liu, S., Wang, S., Xing R.. Preparation and application of a novel silica-supported organic-inorganic hybrid molecular imprinting polymer. Anal. Lett.,2008,41 (10):1811-1817.