Polymer Membrane Ion/Gas/Polyion Sensors: New Frontiers

描述（由申请人提供）：提出了新型阴离子/气体/聚离子选择性聚合物膜/膜基电化学和光学传感器的持续开发、研究和分析应用。研究将建立在几个令人兴奋的突破，在最近一段时间的支持重点是新的化学有用的制造阴离子和气体选择性传感器使用金属卟啉和类似的金属配体配合物在薄聚合物膜。在这些进展中，开发了新的光学和电化学传感器，其在低介电膜中使用Al（III）、Ga（III）和Zr（IV）络合物对氟离子显示出优异的选择性。未来的工作将包括基础和应用研究，并将集中在：1）充分了解各种复合物的有机相连接化学，产生有用的氟化物选择性响应; 2）评估这些物种的氢氧化物或氟离子桥接的二聚体是否可以在聚合物膜内自发形成，以及这种新的二聚体-单体平衡反应是否可以用于氟化物的光学传感; 3）检查防止在聚合物膜内发生二聚体-单体平衡的各种策略，从而制备具有能斯特氟化物响应的电位测定膜电极，以及4）证明这些新的氟化物传感器用于检测城市饮用沃茨中的氟化物，以及用于与酶或金属离子催化剂结合使用以监测有毒氟磷酸盐（例如，神经毒气）。此外，研究将继续评估金属卟啉和salophens是否尚未详细研究（例如，Co（III）、Mn（III）、Sn（IV）、Tl（III）、Sc（III）等）可以在聚合物薄膜内经历二聚体-单体化学反应。如果是这样的话，将努力设计新的和高选择性的基于聚合物膜的光学传感器，用于给定的阴离子（例如，亚硝酸盐、水杨酸盐等），气体（包括CO、NO等）和其它中性物质（例如，醇、胺等）基于这些物质分配到聚合物膜中并将给定的金属卟啉二聚体断裂成单体的能力，产生Soret带的Xmax的大位移。预计该研究计划将继续为分析界提供广泛的新的和/或改进的化学传感器以及新的基于传感器的方法，这些方法将立即应用于基础生物医学研究和现代临床化学和环境测试仪器。此外，鉴于氟离子在生理系统中的潜在高毒性，特别欢迎用于该物种的新的和简单的测量工具。

DESCRIPTION (provided by applicant): The continued development, study, and analytical applications of novel anion/gas/polyion selective polymer membrane/film-based electrochemical and optical sensors are proposed. Research will build upon several exciting breakthroughs made during the most recent period of support focusing on new chemistries useful for fabricating anion and gas selective sensors using metalloporphyrins and similar metal-ligand complexes within thin polymeric films. Among these advances are the development of new optical and electrochemical sensors that display exceptional selectivity toward fluoride ion using Al(lll), Ga(lll) and Zr(IV)-complexes in low dielectric films. Future efforts will include both fundamental and applied studies and will concentrate on: 1) fully understanding the organic phase ligation chemistry of the various complexes that yield useful fluoride selective responses; 2) assessing whether hydroxide or fluoride ion bridged dimers of these species can form spontaneously within the polymeric films and whether this new dimer-monomer equilibrium reaction can be employed for optical sensing of fluoride; 3) examining various strategies to prevent dimer-monomer equilibria from occurring within the polymer films and thereby prepare potentiometric membrane electrodes with Nernstian fluoride response, and 4) demonstrating practical applications of these new fluoride sensors for detecting fluoride in municipal drinking waters, and for use in conjunction with enzymes or metal ion catalysts to monitor toxic fluorophosphates (e.g., nerve gases). In addition, research will continue to assess whether metalloporphyrins and salophens not yet examined in detail (e.g., Co(lll), Mn(lll), Sn(IV), Tl(lll), Sc(lll), etc.) can undergo dimer-monomer chemistry within thin polymeric films. If so, efforts will be made to devise new and highly selective polymer film-based optical sensors for given anions (e.g., nitrite, salicylate, etc.), gases (including CO, NO, etc.) and other neutral species (e.g., alcohols, amines, etc.) based on the ability of such species to partition into the polymer films and break given metalloporphyrins dimers into monomers, yielding a large shift in the Xmax of the Soret band. It is anticipated that this research program will continue to provide the analytical community with a wide array of new and/or improved chemical sensors as well as novel sensor-based methods that will have immediate applications as tools for basic biomedical research and within modern clinical chemistry and environmental test instrumentation. In addition, given the potential high toxicity of fluoride ion in physiological systems, new and simple measurement tools for this species would be especially welcome.