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萘酰亚胺衍生物等新型荧光载体的合成与共价固定及相关光纤化学传感器的研制
Synthesis and Covalent Immobilization of Naphthalimide and Other Derivatives as New-type Fluorescence Carriers for Optical Fiber Chemical Sensor Preparation
【作者】 牛承岗;
【作者基本信息】 湖南大学 , 分析化学, 2002, 博士
【摘要】 本论文主要工作是合成新型具有可共聚端基双键、性能优良的荧光载体,将荧光载体与其它单体在紫外光照下共聚在经过处理的石英或普通玻璃上制成光极膜,而后研究其分析特性及应用。(1) 合成了N-丙基-4-(N-甲基丙烯酰基氧乙基)氨基-1,8-萘酰亚胺(PMEAN),研制出了苦味酸荧光光纤传感器,可间接测定药片中磷酸氯喹和水样中苦味酸的含量。(2) 合成了N-烯丙基-4-(N-2’-羟乙基)氨基-1,8-萘酰亚胺(AHEAN),研制的呋喃妥因传感器可测定药片和尿样中呋喃妥因的含量。(3) 合成了N-烯丙基-4-哌嗪基-1,8-萘酰亚胺(APN),APN对pH的变化具有“开-关”效应,可测定4-10之间的pH值。(4) 合成了N-烯丙基-4-(4’-甲基哌嗪基)-1,8-萘酰亚胺(AMPN)。AMPN也对pH的变化具有“开-关”效应,而且不受离子强度的影响。测定范围pH4. 5-9. 0。(5) 合成了N-甲基丙烯酰氧乙基-苯并硫杂蒽-3,4-二甲酰亚胺,可用来测定丙酮中0-25%(v/v)的水含量。(6) 合成了meso-四(4-烯丙氧基苯基)卟啉,可测定1. 5-5. 0的pH值。 (7) 合成了N-烯丙基咔唑,用研制的强力霉素传感器测定了药片、尿样中强力霉素的含量。此外还合成了若丹明Rh-Al、3,6-二氨基-9-N-烯丙基咔唑、4-甲基-7-烯丙基萘并[1,2-b]吡喃-2-酮,目前尚未用于传感器的研制。
【Abstract】 One of the most important aspects of fluorescence chemical sensor research is searching new fluorescence carriers for molecular recognition. The fluorescence carriers for preparing sensors are limited to a narrow range of chemical compounds and most fluorescence carriers are physically entraped in various membrane materials. Although physical entraping is a simple method for sensor membrane preparation,the leaching of fluorescence carrier is a major disadvantage. A central research topic is searching new fluorescence carriers with high sensitivity,good selectivity,excellent reversibility and stability. Along this line,the author of present thesis paid attention to naphthalimide,carbazole and porphyrin derivatives. The naphthalimide and carbazole derivatives as well as covalently immobilized porphyrins have not been reported to data in the literature.In this thesis,new fluorescence carriers with good properties were synthesized and copolymerized under UV irradiation on the silanized glass or quartz disk and -the sensors prepared were studied. (1) N-propyl-4-(N-methylacryloxy-ethyl)amino-1,8-naphthalimide (PMEAN) was synthesized and used for determination of picric acid. The linear range of the sensor is 9.80x10-7-1.96x10-4 mol I-1. The sensor has been used for indirect determination of chloroquine content in pharmaceutical tablets. (2) N-Allyl-4(N-2’-hydroxyethyl)amino-l,8-napthalimide (AHEAN) was synthesized and utilized for nitrofurantoin assay based on fluorescence quenching. Nitrofurantoin can be determined in the range between 1.00x10-6 and 1.00x10-3mol I-1. The sensor has been applied to the analysis of pharmaceutical and urine samples. (3) N-Allyl-4-piperazinyl-l,8-napthalimide (APN) with proton "off-on" switch behavior was synthesized. The sensor can be used for the determination of pH between 10 and 4 and has been applied to the analysis of water samples. (4) N-Allyl-4-(4’-methyl-piperazinyl)-l,8-napthalimide (AMPN) with proton "off-on" switch behavior was also synthesized. The sensor can be used for determination of pH in the range of pH4.5 - 9.0 and has been applied to the analysis of urine samples. (5) N-(2-methacryloxyethyl) benzo[k,l]thioxanthene-3,4-dicarboximide (MBTD) was synthesized. The sensor can be used for determination of 0-25%(v/v) water content in acetone. (6) Meso-tetra(4-allyloxyphenyl) porphyrin was synthesized. The sensor can be used for determination of pH in the range of pH 1.5 - 5.0 and has been applied to the determination of water samples. (7) 9-N-allyl carazole was synthesized and used for direct determination of doxycycline. The determination range is 6.00x10-7 and 2.00x10-3 mol I-1. The sensor was used in the analysis of pharmaceutical preparations and urine samples. In addition,three fluorescence carriers were synthesized,they are allyl ester of rhodamine Rh-Al,3,6-diamino-9-N-allyl carazole,4-methyl-7-allyloxynaphtho[l,2-b]pyran-2-one and have not been prepared for sensors yet.
【Key words】 Fluorescence chemical sensor; Covalently immobilization; Fluorescence carrier; Naphthalimide derivative; Porphyrin; Carazole;