A novel type of ion-selective nano-optode is proposed, in which a conjugated polymer is used as optical transducer and nanoprobe material. Thus, contrary to most of the proposed optodes, the response does not require presence of pH-sensitive dye in the sensor. The conjugated polymer nanosensor material is in partially oxidized form-it is bearing positive charges and its emission is quenched. The receptor is an optically silent uncharged ionophore selective for the analyte cation. When a binding event occurs, positive charges are formed in the nanosphere, leading to a decrease in the oxidation state of the polymer, in the absence of redox potential change, resulting in increased emission. This general approach herein proposed results in a simple sensor, benefitting from a novel optical transduction mechanism and high lipophilicity of the polymer matrix that results in linear responses over a broad concentration range of analyte. For the model system studied, the linear dependence of emission intensity on the logarithm of analyte (K(+)) concentration was obtained for a broad range from 10(-5) M to 0.1 M.
A novel solid contact type for all-solid-state ion-selective electrodes is introduced, yielding high stability and reproducibility of potential readings between sensors as well as improved analytical performance. The transducer phase herein proposed takes advantage of the presence of porphyrinoids containing the same metal ion at different oxidation states. In contrast to the traditional approach, the compounds of choice are not a redox pair; although they have different oxidation states, they cannot be electrochemically driven one to another. The compounds of choice were cobalt(II) porphyrin and cobalt(III) corrole-both characterized by a high stability of the coordinated metal ions in their respective redox states and electrical neutrality, as well as relatively high lipophilicity. The porphyrinoids were used together with carbon nanotubes to yield transducer layers for ion-selective electrodes. As a result, we obtained a high stability of potential readings of the resulting ion-selective electrodes together with good reproducibility between different sensor batches. Moreover, advantageously the presence of porphyrinoids in the transducer phase results in improvement of the analytical performance of the sensors: linear response range and selectivity due to interactions with membrane components, resulting in tailoring of ion fluxes through the membrane phase. Thus, carbon nanotubes with the cobalt(II) porphyrin/cobalt(III) corrole system are promising alternatives for existing transducer systems for potentiometric sensors.
Ion-selective membranes, as used in potentiometric sensors, are mixtures of a few important constituents in a carefully balanced proportion. The changes of composition of the ion-selective membrane, both qualitative and quantitative, affect the analytical performance of sensors. Different constructions and materials applied to improve sensors result in specific conditions of membrane formation, in consequence, potentially can result in uncontrolled modification of the membrane composition. Clearly, these effects need to be considered, especially if preparation of miniaturized, potentially disposable internal-solution free sensors is considered. Furthermore, membrane composition changes can occur during the normal operation of sensors—accumulation of species as well as release need to be taken into account, regardless of the construction of sensors used. Issues related to spontaneous changes of membrane composition that can occur during sensor construction, pre-treatment and their operation, seem to be underestimated in the subject literature. The aim of this work is to summarize available data related to potentiometric sensors and highlight the effects that can potentially be important also for other sensors using ion-selective membranes, e.g., optodes or voltammetric sensors.
We report for the first time on in situ transduction of electrochemical responses of ion-selective electrodes, operating under non-zero-current conditions, to emission change signals. The proposed novel-type PVC-based membrane comprises a dispersed redox and emission active ion-to-electron transducer. The electrochemical trigger applied induces a redox process of the transducer, inducing ion exchange between the membrane and the solution, resulting also in change of its emission spectrum. It is shown that electrochemical signals recorded for ion-selective electrodes operating under voltammetric/coulometric conditions correlate with emission intensity changes recorded in the same experiments. Moreover, the proposed optical readout offers extended linear response range compared to electrical signals recorded in voltammetric or coulometric mode.
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