【作者】 谢增鸿；

【导师】 陈国南；

【作者基本信息】 福州大学 ， 物理化学， 2005， 博士

【摘要】 光导纤维光波导技术与高灵敏的荧光分析法相结合的光纤化学传感器（fiber-optical chemical sensors，FOCS）的发展，为原位、瞬时、高灵敏度的化学信息获取展示了良好的前景，是目前分析科学发展的一个重要研究方向之一。传感探头是光纤化学传感器中最重要的组成部分，它对分析对象进行选择性的识别的同时承担着光学信号表达的功能。因此，传感探头的制备是关键。然而，常规的传感探头通常通过将识别元件以传感膜的形式披覆在光纤的端部而获得，在使用过程中传感膜往往存在着指示剂负载量有限、光漂白以及洗脱等问题，从而影响了光纤化学传感器的使用寿命。本论文致力于一种新的化学传感探头的探索研究，发展了一种新型的多孔塑料光纤传感探头。该技术采用高分子聚合技术，将敏感指示剂以包埋或共价结合的方式直接聚合于整体聚合物光纤中，惰性溶剂在聚合过程中不参与化学反应，而留下相互交联的多孔结构。待测的分析对象进入多孔塑料光纤传感探头内部相互交联的微孔结构，与敏感指示剂反应，从而引起敏感指示剂光学性质的变化。 本论文总共分为五章，第一章介绍光纤化学传感器的发展、光纤化学传感器的原理、传感探头指示剂的固定方法，最后介绍本论文的主要工作以及本论文的特色与创新之处。第二章介绍了多孔塑料光纤传感探头的制备原理、制备过程、制备原料，并详细探讨了多孔塑料光纤传感探头制备过程的影响因素。第三章研究了以具有憎水性能的甲基丙烯酸甲酯或苯乙烯为单体、双甲基丙烯酸二乙二醇酯为交联剂、藻红或氨基荧光素为荧光指示剂，采用交联共聚技术制备对氨敏感的多孔塑料光纤传感探头；详细考查了使用不同交联度、不同致孔剂量、不同指示剂浓度所制备的多孔塑料光纤传感探头对氨的响应情况，并对传感探头的稳定性、重现性、可逆性等响应性能进行了讨论。由于多孔塑料光纤传感探头的憎水性，溶液中的pH不干扰氨的测定。在最佳的制备条件下，以藻红为指示剂的多孔塑料光纤传感探头对氨的响应范围为2×10－4mol·L－1～9.1×10－3mol·L－1，以氨基荧光素为指示剂的多孔塑料光纤传感探头对氨的响应范围为1～20 ppm。第四章研究了以具有亲水功能基团-COOH的甲基丙烯酸为单体，双甲基丙稀酸二乙二醇酯为交联剂，庚烷为致孔剂，对pH敏感的荧光染料曙红为指示剂，合成具有亲水性能的多孔塑料光纤传感探头，并考察多孔塑料光纤传感探头对pH的响应特性。该传感探头在pH0.0～3.0范围内对pH有较好的响应。第五章主要研究以憎水性能好、透气性能强的甲基丙烯酸-2，2，3，3-四氟代丙酯（TFPM）、甲基丙烯酸异丁酯（IBM）为混合功能单体，二甲基丙烯酸二乙二醇酯(DGDA)为交联剂，钌(Ⅱ)-三-4,7-二苯基-1,10-菲咯啉高氯酸盐复合物为指示剂，采用交联共聚技<WP=5>术制备多孔塑料光纤传感探头，研究传感探头对溶解氧的响应情况，并考查了使用不同交联度、不同致孔剂量、不同指示剂浓度所制备的传感探头对溶解氧的响应性能。溶解氧在0～10ppm范围内，该多孔塑料光纤传感探头的荧光猝灭比值与溶解氧浓度成一线性关系，95%响应时间约1.50min。本章还对传感探头指示剂泄漏、重现性、可逆性等性能进行深入讨论。更多还原

【Abstract】 The development of fiber-optical chemical sensors (FOCS), which is the combination of fiber wave-guide technology and fluorescence analysis method， provides prosperously future for the acquisition of on-line, fast and highly sensitive chemical information. Today, FOCS becomes one of the most important research orientation of analytical science. The probe, which is the hard core of FOCS, can selectively identify the analyte as well as assumes the expression of optics signal. So the preparation of probe is the crux for the development of FOCS. Generally, the probe was achieved by covering the sensitive membrane on the end of fiber, and the lifetime of FOCS was restricted by the insufficiency, bleaching and leakage of indicator in the probe.In this thesis, a new porous plastic fiber optical probe was developed. The indicator was embedded or covalently reacted with the monomer in the porous polymer monolith fiber by copolymerization, while inert solvent didn’t react during the course of polymerization and a cross-linking porous network came into being inside the probe. When the analyte passed through the pore and reacted with the indicator inside the probe, the optical character of indicator in the probe was changed. This thesis includes five chapters. In Chapter one, the development and principle of FOCS, and the load of indicator in probe were introduced. The main work and innovation of this thesis were brought forward in the end of chapter.In chapter two, the principle, material and the course of preparation of porous plastic fiber optical probe were dissertated and the influence factors of the preparation were throughly discussed.In chapter three, the porous plastic fiber optical probe for ammonia was prepared by copolymerization of hydrophobic methyl methacrylate or styrene as monomer, diethylene glycol dimethacrylate as cross-linking reagent and tetra-iodo-fluorescein or amidofluorescein as fluorescent indicator. The response <WP=7>character for ammonia of porous plastic fiber optical probe with different cross-linking degree, different amount of porogen and indicator were particularly investigated. And the stability, reproduction and reversibility of the probe were also discussed. Since the porous plastic fiber optical probe was hydrophobic，the pH didn’t interfere the determination of ammonia. Under the optimal condition, the calibration curve of the porous plastic fiber probe ranged from 2.0×10－4mol/L~9.1×10－3mol/L range of and from 1 ppm~ 20 ppm of ammonia concentration for the fluorescent indicator tetra-iodo-fluorescein or amidofluorescein, respectively. In chapter four, the porous plastic fiber optical probe for pH was prepared by copolymerization of hydrophile methacrylic acid as monomer, diethylene glycol dimethacrylate as cross-linking reagent, heptane as porogen and fluorescent dye Eosin as indicator. And the response characteristic of probe for pH was studied. Under the optimal condition, the calibration curve covered the range of pH0.0~3.0.In chapter five, the porous plastic fiber optical probe for dissolved oxygen was prepared by copolymerization of hydrophobic and ventilative 2，2，3，3-tetrafluoropropyl methacrylate and butyl methacrylate as admixture monomer, diethylene glycol dimethacrylate as cross-linking reagent and tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) perchlorate as fluorescent indicator. The response characteristic for dissolved oxygen of porous plastic fiber optical probe with different cross-linking degree, different amount of porogen and indicator were particularly investigated. Under the optimal condition, the calibration curve ranged from 0～10 ppm of dissolved oxygen concentration and t95 was 1.5 min. The leakage of indicator, reproduction and reversibility of the probe were also discussed in this chapter.更多还原