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。研究将建立在最近支撑期取得的几项令人兴奋的突破的基础上，重点放在新的化学物质上，这些化学物质可用于在聚合物薄膜中使用金属卟啉和类似的金属-配体络合物来制造阴离子和气体选择传感器。这些进展包括新型光学和电化学传感器的开发，这些传感器利用低介电薄膜中的Al(111)、Ga(111)和Zr(IV)络合物对氟离子表现出极高的选择性。未来的努力将包括基础和应用研究，并将集中在：1)充分了解产生有用的氟选择反应的各种络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联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膜电极；以及4)展示这些新型氟化物传感器在城市饮用水氟检测中的实际应用，并与酶或金属离子催化剂一起用于监测有毒的氟磷酸盐(如神经气体)。此外，研究将继续评估金属卟啉和三苯基苯是否尚未得到详细检查(例如，Co(111)、Mn(111)、Sn4(IV)、Tl(111)、Sc(111)等)。可在聚合物薄膜中进行二聚-单体化学。如果是这样的话，将努力为给定的阴离子(例如，亚硝酸盐、水杨酸盐等)、气体(包括CO、NO等)设计新的、高选择性的聚合物薄膜光学传感器。和其他中性物种(例如，醇、胺等)基于这些物种分配到聚合物膜中并将给定的金属卟啉二聚体分解成单体的能力，导致Soret带的xmax发生较大移动。预计这项研究计划将继续为分析界提供一系列新的和/或改进的化学传感器以及基于传感器的新方法，这些方法将立即作为基础生物医学研究的工具，并在现代临床化学和环境测试仪器中得到应用。此外，考虑到氟离子在生理系统中的潜在高毒性，针对这一物种的新的简单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.