SENSORS: Multi-Anion Sensing by Conductive Polymers with Dual Mode of Signal Transduction

这一提议的目标是开发和研究新型的、固有导电的聚合物薄膜，该薄膜将用于对无机阴离子的选择性传感，重点是与磷酸盐和磷酸盐相关的物种。磷酸盐和膦酸根离子水平的检测和定量测量是药物检测和药理学(药代动力学)研究以及环境监测的重要要求。这些存在于化肥和医药中的阴离子的传感针对的是水环境和低浓度(10-6mol/L)。将开发能够通过光学(颜色/发射)和电学性质的变化同时对分析物的存在进行反应的传感器材料。两种独立的信号转导模式的结合将提高传感过程的选择性和可靠性。这将通过制备新型的聚噻吩基聚合物材料来实现，该材料将阴离子选择性受体集成到聚合物的pi共轭主链中。在PI以前的研究中积累的关键知识将被用于制备含有合适的受体和可电聚合的噻吩衍生物的单体。这些传感器单体将在透明电极表面进行电化学聚合。这种涂有阴离子传感器材料的透明电极将被用于制备光谱电化学池，这将允许使用两种信号转导模式来研究阴离子结合：光学和电学性质的变化。这种双模式信号转导有望提高批发过程的准确性，增强特异性，并使这些材料能够在多阴离子环境中进行阴离子传感。在多阴离子环境中，使用可单独寻址的透明微电极和带有不同受体的多个沉积材料，可以实现可靠的阴离子传感；或者，通过两个或多个带有不同受体单元的传感器单体的共聚，可以获得类似的效果。这些涂有传感器的电极将被用于制造传感器设备，并将在多分析物环境中进行测试。拟议的研究具有不同的智力价值。能够在低浓度的极性/水溶液中检测阴离子底物的聚合物材料很少。因此，将成功的分子传感器应用到聚合物材料中的努力是可取的，这可能有助于开发性能更好的耐蚀/稳定材料。在这方面特别重要的是通过同时实施两种独立的信号转导模式来提高传感过程的可靠性和准确性的想法。这可能允许对阴离子底物进行可靠的传感，否则很难传感。通过同时改变两个变量来检测阴离子的方法可能允许检测多个阴离子分析物。这一点特别重要，因为尽管需求很大，但到目前为止还没有成功地制备出既能提供高选择性又能实现多分析物传感的材料和器件。就更广泛的影响而言，这项PI想要强调的是，拟议的研究将通过研究新的传感器材料来促进常识的发展。所提出的多阴离子传感器将在广泛的应用中非常有用，主要是医疗和环境，例如，允许精确地监测药物代谢，从而刺激新的药物代谢分析的发展。这种新型导电聚合物的开发和研究具有双重信号转导模式，可用于检测阴离子多分析物，代表着一个新兴且影响深远的研究和技术领域的风险。这位PI的团队还将积极参与一项跨学科的讨论，重点是通过出版和积极参与科学会议的阴离子传感的各个方面。最后但并非最不重要的是，更广泛的社会将从教育的进步中受益，从而为合格劳动力的专业培训做出贡献。

The objective of this proposal is the development and study of novel, inherently conductivepolymer thin films that will be used for selective sensing of inorganic anions with emphasis onphosphate- and phosphonate-related species. The detection and quantitative measurement of levels ofphosphate and phosphonate anions is an important requirement for drug testing and pharmacological(pharmacokinetic) studies as well as environmental monitoring. The sensing of these anions, found infertilizers and pharmaceuticals, is aimed at aqueous environment and low concentrations ( 10 -6 mol/l).Sensor materials capable of reacting to the presence of analyte by change of optical(color/emission) and electrical properties in a simultaneous regime will be developed. The combination oftwo independent modes of signal transduction will improve the selectivity and reliability of the sensingprocess. This will be accomplished by preparing novel polythiophene-based polymer materials withanion-selective receptors integrated into the pi-conjugated backbone of the polymer. The criticalknowledge amassed during the PI's previous studies will be used to prepare monomers bearing suitablereceptors and electropolymerizable thiophene derivatives. These sensor monomers will beelectrochemically polymerized on the surface of transparent electrodes. Such transparent electrodescoated with anion sensor material will be used to fabricate spectroelectrochemical cells, which will allowfor investigation of anion binding using two modes of signal transduction: changes in optical andelectrical properties. The two-mode signal transduction is expected to increase the accuracy of the wholesensing process, enhance specificity and make these materials capable of anion sensing in multi-anionenvironments. Reliable anion sensing in multi-anion environments will be achieved by using individuallyaddressable transparent microelectrodes with multiple deposited materials bearing different receptors.Alternatively, similar effect may be achieved by copolymerization of two or more sensor monomersbearing different receptor units. These sensor-coated electrodes will be used to build sensor devices andwill be tested in multi-analyte environments.The intellectual merit of the proposed research is diverse. Polymer materials capable of sensingof anionic substrates in polar/aqueous solutions at low concentrations are rare. Efforts towardimplementing successful molecular sensors into polymer materials, which may allow the development ofrobust/stable materials with improved performance, are therefore desirable. Particularly important in thisregard is the idea of improved reliability and accuracy of the sensing process by simultaneousimplementation of two independent modes of signal transduction. This may allow for reliable sensing ofanionic substrates that are otherwise difficult to sense. The approach of detecting the anion by change oftwo variables in a simultaneous regime may allow for sensing of multiple anionic analytes. This isparticularly important because, despite the great need, materials and devices that would provide both highselectivity and allow for multi-analyte sensing have not been successfully prepared so far.In terms of the broader impacts, this PI would like to emphasize that the proposed research willserve for the advancement of general knowledge by investigating novel sensor materials. The proposedmulti-anion sensors would be highly useful in a wide variety of applications, mostly medical andenvironmental, for example to allow for a precise monitoring of drug metabolization thus stimulate adevelopment of novel drug-metabolization assays. The development and investigation of such novel,conductive polymers with dual mode of signal transduction for sensing anionic multi-analytes representsa venture into an emerging and far reaching area of research and technology. This PI's team will also takeactive part in an interdisciplinary discussion focused on various aspects of anion sensing throughpublication and active participation in scientific meetings. Last but not least, the broader community willbenefit through the advancement of education thus contributing to professional training of qualifiedworkforce.