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/多离子选择性聚合物膜/薄膜电化学和光学传感器的持续开发、研究和分析应用。研究将建立在最近支持期间取得的几项令人兴奋的突破之上，重点关注用于制造阴离子和气体选择性传感器的新化学物质，这些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薄膜中。这些进展包括利用Al（lll）、Ga（lll）和Zr（IV）配合物在低介电薄膜中开发出对氟离子具有特殊选择性的新型光学和电化学传感器。未来的工作将包括基础研究和应用研究，并将集中于：1)充分了解产生有用氟化物选择反应的各种配合物的有机相连接化学；2)评估这些物种的氢氧化物或氟离子桥接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的光学传感；3)研究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Nernstian氟化物响应的电位膜电极；4)展示这些新的氟化物传感器的实际应用，用于检测城市饮用水中的氟化物，并与酶或金属离子催化剂一起使用，以监测有毒的氟磷酸盐（例如，神经毒气）。此外，研究将继续评估尚未详细检查的金属卟啉和salophens(例如，Co(ll), Mn(ll), Sn(IV), Tl（ll), Sc（ll）等）是否可以在薄聚合物薄膜内进行二聚体单体化学反应。如果是这样的话，人们将努力设计出新的、高选择性的基于聚合物薄膜的光学传感器，用于给定的阴离子（如亚硝酸盐、水杨酸盐等）、气体（包括CO、NO等）和其他中性物质（如醇、胺等），基于这些物质进入聚合物薄膜并将给定的金属卟啉二聚体分解成单体的能力，从而产生Soret波段的Xmax的大偏移。预计该研究项目将继续为分析界提供广泛的新型和/或改进的化学传感器，以及新颖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，考虑到氟离子在生理系统中的潜在高毒性，新的和简单的测量工具将特别受欢迎。

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.