【作者】 王樱蕙；

【导师】 李斌；

【作者基本信息】 中国科学院研究生院（长春光学精密机械与物理研究所） ， 凝聚态物理， 2011， 博士

【摘要】 随着人类活动和全球经济的快速发展,我们赖以生存的环境遭到了前所未有的破坏。工业化污染的加剧,不但导致空气质量逐年下降,而且使各种重金属污染物,特别是高毒性的汞离子,通过不同的渠道进入水体中,给人类的生产、生活带来了巨大的危害。因此,对衡量空气质量主要指标的氧浓度和痕量汞离子的测定对于分析化学、生物化学、医疗诊断、环境监测等研究领域均有着十分重要的意义。近年来,以荧光作为检测信号的荧光化学传感器被广泛应用于检测氧和汞离子的浓度。本论文就是从荧光探针分子和纳米基质材料的设计、制备两方面入手,利用简单的静电纺丝、水热等方法制备了多种纳米复合传感材料,并详细研究了纳米复合传感材料的结构、传感性能、稳定性及重复使用性。本论文取得的主要成果如下:（1）设计合成了一种发光性能优异的铜（Ⅰ）配合物,并首次利用简单的静电纺丝方法将其制备成为复合纳米纤维氧传感材料。该材料具有高的灵敏度(I₀/I₁₀₀ = 15.56),短的响应及还原时间（t↓（s） = 7 and t↑（s） = 14）和近乎线性的Stern–Volmer关系曲线。这是目前基于廉价金属配合物氧传感材料报道的最佳性能。该材料优异的传感性能、低廉的价格、简单的制备方法以及环境友好等特点使其具有潜在的商业应用价值。（2）设计合成出了一种新颖的稀土铕（Ⅲ）配合物,并利用简单的静电纺丝方法将其制备成为复合纳米纤维氧传感材料。该材料具有短的响应及还原时间（t↓（s） = 5 and t↑（s） = 8）,好的稳定性和重复使用性。该材料大的比表面积、及多孔的结构,有利于氧气的扩散及与配合物的碰撞,显著提高了材料的灵敏度。其灵敏度由几乎没有应用价值的不足2,提高至可实用化的3.38,为目前国际上基于稀土配合物类光学氧传感器的最高值。（3）利用化学键合的方法将芘的衍生物组装到介孔分子筛SBA^-15中,将其制备成为纳米复合传感材料(Py-SBA^-15)。该材料对重金属汞离子具有好的选择性、短的响应时间和高的灵敏度,检测限可达1.7×10^-7 gmL^-1。并且其荧光强度表现出对汞离子的线性响应,可以实现即时的检测汞离子浓度。另外,该材料可以实现多次的重复使用。基于以上原因,该材料有望应用于检测水中的汞离子浓度。（4）设计合成了一种新颖的罗丹明类衍生物,该材料不但可以用于检测重金属汞离子,还可以利用其对重金属汞离子和铜离子的不同荧光响应,将其构建成为分子键盘锁。只有输入正确的密码时,体系呈现强的荧光,键盘锁被打开;密码错误时,体系无荧光,且出现警告信号。该键盘锁不但实现了分子水平的信息保护,而且还可以应用到未来分子计算机的安全器件上,用于授权用户、识别产品身份等领域。（5）利用溶胶-凝胶的方法制备了一系列有机改性的有机-无机杂化的稀土材料,并研究了该系列材料的光学性质。通过改变有机改性硅酸酯和正硅酸乙酯的比例,荧光强度迅速增加,当VTES:TEOS = 4:6时,该材料的荧光强度是纯铕配合物的2.4倍,是未改性材料的3.3倍。同时,材料的量子效率和发光热稳定性也显著提高。更多还原

【Abstract】 With the rapid development of global economy, our living environment has been severely destroyed. The increase of industrial pollution, not only leads to air quality decline, but also makes sorts of heavy metal pollutants enter into the water through different ways, especially high toxic mercury ion, which resulted in tremendous harm to human life. Therefore, the determination of oxygen and trace mercury ions concentration has important significance in the field of analytical chemistry, biochemistry, medical diagnosis and environmental monitoring. In recent years, chemosensors utilizing fluorescence intensity as their response signal have been developed to be useful tools for sensing various analytes, such as oxygen and mercury ions. Surrounding the design and synthesis of the ?uorescent probes and nanomatrix materials, this dissertation presents a systematic research about the synthesis of the nanocomposite sensing materials by electrospinning or hydrothermal synthesis method. Detailed analyses on the structure, stability, regenerative ability and sensing performances of the final obtained nanocomposite sensing materials are investigated. The major achievement obtained is as follow:（1） A novel Cu（Ⅰ） complex [Cu（POP）phencarz]BF4 was design and synthesized. Then it was incorporated into polystyrene （PS） matrixes and electrospun into composite nanofibrous membranes using the simple electrospinning method. The optical oxygen sensing properties of [Cu（POP）phencarz]BF₄/PS composite nanofibrous membranes were investigated. They showed high sensitivity (I₀/I₁₀₀ = 15.56), good linear Stern-Volmer characteristics （R² = 0.9966） and short response and recovery time （t↓（s） = 7 and t↑（s） = 14）. These results represent the best values reported for oxygen sensors based on Cu（Ⅰ） complexes. The outstanding performances, the simple and versatile preparing method and environmental-friendly and economical attraction endow this kind of composite nanofibrous membrane with the potential for commercial application in oxygen sensors.（2） A novel Eu（Ⅲ） complex of [Eu（TTA）3phencarz] was design and synthesized. Then it was incorporated into polystyrene （PS） matrixes and electrospun into composite nanofibrous membranes using the simple electrospinning method. These materials showed good operational stability, reproducibility and short response and recovery time （t↓（s） = 5 and t↑（s） = 8）. The sensitivity is up to 3.38, which represents the best values reported for oxygen sensors based on Eu（Ⅲ） complexes. The high surface area-to-volume ratio and porous structure of the electrospun nanofibrous membranes are urged to be responsible for the outstanding performances.（3） A novel nanocomposite sensing material was prepared through the functionalization of mesoporous silica （SBA-15） covalently grafted with a pyrene derivative. The obtained material （Py-SBA-15） demonstrates a high selectivity for Hg²⁺ ions in the presence of other metal ions. A good linearity between the fluorescence intensity of Py-SBA-15 and the concentration of Hg²⁺ ions is constructed, and a satisfactory detection limit of 1.7×10^-7 gmL^-1 is obtained. More importantly, Py-SBA-15 shows good regenerative ability. These results indicate that this nanocomposite sensing material could be a promising ?uorescence chemosensor for detecting Hg²⁺ ions.（4） A novel fluorescent chemosensor based on rhodamine derivative has been designed and synthesized for detection of Hg²⁺ ions. Moreover, this‘Off–On’-type fluorescent sensor could successfully mimic a molecular level keypad lock in the presence of Cu²⁺ ions. Only a specific sequence of inputs, i.e. the correct password, results in strong fluorescence emission at 555 nm, which can be used to“open”this molecular keypad lock. Therefore, this molecular keypad lock has the potential for applying in security devices, which would be used to authorize a user, to verify authentication of a product, or to initiate a higher process.（5） A series of novel organic-inorganic hybrid materials with a Eu（Ⅲ） complex covalently bonded into the vinyl modified silica networks have been successfully assembled through a sol-gel process. The luminescence properties of VTES/TEOS composite hybrid materials were systematically studied. The results indicate that the luminescence intensity of VTES/TEOS composite hybrid material by optimizing the molar ratio of VTES to TEOS （VTES:TEOS = 4:6） is enhanced by 3.3 and 2.4 times compared with TEOS-derived hybrid material and pure [（C₂H₅）₄N][Eu（DBM）₄], respectively. In addition, the thermal stability of the emission was also improved considerably.更多还原