The continued development, study, and bioanalytical applications of novel polyion and anion selective polymer membrane/film-based electrochemical and optical sensors are proposed. Research during the next phase of this long-term project will build upon several significant discoveries/advances made during the most recent project period relating to potentiometric polyion sensing and new chemistries for anion-selective sensors. These include dramatically lowering the detection limits toward biomedically important polyions (e.g., heparin, protamine, etc.) via use of a novel rotating potentiometric membrane electrode configuration, and 2) uncovering a unique hydroxide ion bridged dimer/monomer equilibrium that can exist for certain metalloporphyrins when used as ionophores in organic polymer films for devising anion sensing electrodes. Future efforts will include both fundamental and applied studies in both the polyion and anion sensing areas. Specific goals for the polyion sensor efforts include: a) better understanding the nature (size, stoichiometry, etc.) of the ion-exchanger/polyion complexes that form within the polymer membranes used to fabricate such devices; b) demonstrating broader bioanalytical applications of the new, more sensitive rotating polyion sensing membrane electrode configuration; c) investigating the use of polyion sensors (including rotating arrangement) to detect polycationic dendrimers and their interaction with DNA; and d) further development of a completely new and rapid homogeneous immunoassay method for detecting of small, clinically and environmentally important analytes using polyions as labels. In the area of anion sensors, efforts will focus on establishing which metalloporphyrins can spontaneously form hydroxide ion bridged dimer structures within polymeric films, and determining how these reactions affect the response properties of anion selective electrodes formulated with such ionophores. In addition, studies will be undertaken to utilize this novel chemistry to devise completely new polymer film-based optical sensors for anions and neutral species (amines, gases, etc.) based on the ability of such ligating species to break metalloporphyrins dimers into monomers within the organic films, yielding a large shift in the lambdamax of the Soret band. Investigations of electrochemical anion sensors based on a new type of lipophilic dendntic anion-exchanger structure are also proposed. It is anticipated that this research 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 research and within modem clinical and environmental test instrumentation.

National Institute of Health (NIH)
National Institute of Biomedical Imaging and Bioengineering (NIBIB)
Research Project (R01)
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Special Emphasis Panel (ZRG1-BECM (01))
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Moy, Peter
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University of Michigan Ann Arbor
Schools of Arts and Sciences
Ann Arbor
United States
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Wang, Xuewei; Zhang, Qi; Nam, Changwoo et al. (2017) An Ionophore-Based Anion-Selective Optode Printed on Cellulose Paper. Angew Chem Int Ed Engl 56:11826-11830
Wang, Xuewei; Qin, Yu; Meyerhoff, Mark E (2015) Paper-based plasticizer-free sodium ion-selective sensor with camera phone as a detector. Chem Commun (Camb) 51:15176-9
Bell-Vlasov, Andrea K; Zajda, Joanna; Eldourghamy, Ayman et al. (2014) Polyion selective polymeric membrane-based pulstrode as a detector in flow-injection analysis. Anal Chem 86:4041-6
Yang, Si; Wo, Yaqi; Meyerhoff, Mark E (2014) Polymeric optical sensors for selective and sensitive nitrite detection using cobalt(III) corrole and rhodium(III) porphyrin as ionophores. Anal Chim Acta 843:89-96
Yang, Si; Meyerhoff, Mark E (2013) Study of Cobalt(III) Corrole as the Neutral Ionophore for Nitrite and Nitrate Detection via Polymeric Membrane Electrodes. Electroanalysis 25:2579-2585
Bell, Andrea K; Hofler, Lajos; Meyerhoff, Mark E (2012) Revisiting the Response Mechanism of Polymeric Membrane Based Heparin Electrodes. Electroanalysis 24:53-59
Gemene, Kebede L; Meyerhoff, Mark E (2012) Selectivity Enhancement for Chloride Ion by In(III)-Porphyrin-Based Polymeric Membrane Electrode Operated in Pulsed Chronopotentiometric Mode. Electroanalysis 24:643-648
Kang, Youngjea; Gwon, Kihak; Shin, Jae Ho et al. (2011) Highly sensitive potentiometric strip test for detecting high charge density impurities in heparin. Anal Chem 83:3957-62
Gemene, Kebede L; Meyerhoff, Mark E (2011) Detection of protease activities by flash chronopotentiometry using a reversible polycation-sensitive polymeric membrane electrode. Anal Biochem 416:67-73
Gemene, Kebede L; Meyerhoff, Mark E (2010) Reversible detection of heparin and other polyanions by pulsed chronopotentiometric polymer membrane electrode. Anal Chem 82:1612-5

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