纯水相中基于聚合物胶束的新型氟离子荧光化学传感器

Owing to the considerable significance of fluoride anions for health and environmental issues, it is of great importance to develop methods that can rapidly, sensitively and selectively detect the fluoride anions in aqueous media and in such biological samples as urine and serum, as well as inside live cells in terms of human health and environment protection. Fluorescent chemosensors with high specificity,sensitivity,and ease of operation have received increasing interest. A variety of fluorescent chemosensors for fluoride anions have been developed so far, however, most of them can only work in organic solvents because of the strong solvation of probe molecules in aqueous solution. The objectives of this program are to (a)synthesis a series of fluorescent chemosensors for fluoride anions based on chromophores such as xanthenes, boron dipyrromethene difluoride(BODIPY), and naphthalimide; (b)prepare numbers of novel biocompatible polymeric micells which incorporated into the sensing system to ensure water solubility and to enhance biocompatibility. (c)investigate the detection properties of fluoride anion and disscuss the recognition mechanisms. The commonly adopted sensing strategy involves supramolecular interactions sucn as anion-π interactions , hydrogen bonding and Lewis acid/base interactions. However, most of these sensors are operative only in organic solvents to detect tetrabutylammonium fluoride rather than inorganic fluoride salts, because water would compete significantly with the probe for the anion. The appearance of reaction-based chemosensor system has provided a new method for detecting fluoride anions. Polymeric micelles self-assembled from amphiphilic bolck copolymers have been developed as carriers to improve the pharmacokinetic and efficacy of typical anticancer drugs. The sensors exhibit fast response to the fluoride anions with low detection limit,good selectivity and good biocompatiability are expected have the potential for application in the detection for fluoride anions in water quality monitoring as well as in diagnosis of fluoride poisoning.

由于氟离子独特的生物和化学性质，无论是在生物体中还是环境中，在纯水相中对氟离子进行选择性识别和检测都具有重要的研究意义。光化学传感器以其高选择性、高灵敏度、简便快捷、易于实时原位监测等优点，受到了人们的广泛关注。目前所报道的氟离子荧光传感器大多数都只能在有机溶剂中或含水体系中工作，本项目拟设计合成以氧杂蒽、BODIPY、和NDI等荧光团为发光体的新型化学反应型氟离子传感分子，并且在氟离子荧光化学传感分子体系中引入聚合物胶束，以解决长久以来存在的无法在纯水体系中进行识别过程的问题。聚合物胶束已经被证明具有良好的生物相容性，并且由于其具有低毒性，可以为下一步细胞中氟离子的识别成像打下基础。通过对聚合物胶束氟离子荧光化学传感分子进行光谱研究，为更有效地设计在生物、医学、环境科学等领域具有实际应用价值的新型荧光传感器提供必要的理论指导，为进一步发展出实用传感器件打下坚实基础。

氟是人体所必需的微量元素，适量的氟化物摄入可以预防龋齿，治疗骨质疏松症。但是高浓度的氟化物摄入会导致氟斑牙、氟骨症、尿石症以及癌症等疾病。相对于传统的离子色谱法、选择电极法等方法，荧光化学传感器法具有高灵敏度、低检测限、快速简便、成本低及抗干扰能力强等优点，还可以进行生物荧光成像，检测生物体内和细胞内的氟离子。为了实现在纯水中对氟离子的识别，我们主要采取两种策略：一是利用F127增溶胶束对有机小分子荧光传感器进行增溶；二是引入水溶性链段，制备具有水溶性的共聚物。本项目基于苯并噻唑和3-羟基黄酮发光团进行了荧光传感器的设计合成，利用荧光光谱、紫外光谱及核磁共振等手段对产物的氟离子识别性能进行了系统的研究。利用增溶胶束实现了对有机小分子荧光传感器的增溶，但在纯水相中的氟离子识别效果较差。通过引入水溶性链段从而制备具有水溶性的共聚物，取得了一定进展，将来仍需完成识别性质的研究，该部分工作仍需继续深入研究。