%0 Generic %9 Doctoral Dissertation %A Kim, Yushin %D 2014 %F pittir:21025 %K Voltammetric ion sensor %T Development of Voltammetric Double-Polymer-Modified Electrodes for Nanomolar Ion Detection for Environmental and Biological Applications %U http://d-scholarship-dev.library.pitt.edu/21025/ %X Qualitative and quantitative electrochemical methods for trace ion analysis of organic and inorganic species with environmental and biological attention have been developed and reported during past decades. The development of fast and accurate electrochemical methods is critical for field applications with various blocking contaminants. Voltammetric method is attractive not only to analyze selective ion species due to its characteristic based on ion lipophilicity, but also to lower the limit of detection by combining with stripping analysis. In my PhD work, I have developed and studied a highly selective and sensitive electrochemical method that can be used to characterize fundamental transport dynamics and to develop electrochemical sensors at liquid/liquid interfaces based on electrochemically-controlled ion transfer and recognition. The understanding of the kinetic and thermodynamic properties of the voltammetric ion transfer through polymer-modified ion-selective electrodes leads to realize the highly selective and sensitive analytical method. The ultrathin polymer membrane is used to maximize a current response by complete exhaustion of preconcentrated ions. Therefore, nanomolar detection is achieved and confirmed by a thermodynamic mechanism that controls the detection limit. It was also demonstrated experimentally and theoretically that more lipophilic ionic species gives a significantly lower detection limit. The voltammetric method was expanded into inexpensive and disposable applications based on pencil lead modified with the thin polymer membrane. In the other hand, micropipet/nanopipet voltammetry as an artificial cell membrane was used to study the interface between two immiscible solutions for environmental and biomedical applications. It is very useful to get quantitative kinetic and thermodynamic information by studying numerical simulations of ion transfer and diffusion. Molecular recognition and transport of heparin and low-molecular-weight heparin drove by hydrophobic receptors were examined thermodynamically and demonstrated that the selectivity for sensor applications is influenced by the interfacial interactions. Also, we found that a new heparin ionophore enables voltammetric extraction of heparins with various average molecular weights.