Poly(3-octylthiophene) as solid contact for ion-selective electrodes: contradictions and possibilities

The hydrophobic conductive polymer, poly(3-octylthiophene) (POT), is considered as uniquely suited to be used as an ion-to-electron transducer in solid contact (SC) ion-selective electrodes (ISEs). However, the reports on the performance characteristics of POT-based SC ISEs are quite conflicting. In this study, the potential sources of the contradicting results on the ambiguous drift and poor potential reproducibility of POT-based ISEs are compiled, and different approaches to minimize the drift and the differences in the standard potentials of POT-based SC ISEs are shown. To set the potential of the POT film, it has been loaded with a 7,7,8,8-tetracyanoquinodimethane (TCNQ/TCNQ·−) redox couple. An approximately 1:1 TCNQ/TCNQ·−ratio in the POT film has been achieved through potentiostatic control of the potential of the redox couple-loaded conductive polymer. It is hypothesized that once the POT film has a stable, highly reproducible redox potential, it will provide similarly stable and reproducible interfacial potentials between the POT film and the electron-conducting substrate and result in SC ISEs with excellent reproducibility and potential stability. Towards this goal, the potentials of Au, GC, and Pt electrodes with drop-cast POT film coatings were recorded in KCl solutions as a function of time. Some of the POT films were loaded with TCNQ and coated with a K+-selective membrane. The improvement in the potential stabilities and sensor-to-sensor reproducibility as a consequence of the incorporation of TCNQ in the POT film and the potentiostatic control of the TCNQ/TCNQ·−ratio is reported

Equilibration Time of Solid Contact Ion-Selective Electrodes

Papers published on ion-selective electrodes (ISEs) generally report on the performance characteristics of these devices after long, extensive conditioning. Conditioning refers to the equilibration of the ion-selective electrode in an aqueous solution before the measurement of the sample. The requirement for long and repeated conditioning is a significant burden in a variety of applications, for example, single-use sensors aimed for in vivo or field applications and solid contact (SC) ISEs, which were developed to provide simple, mass-produced sensors that have the potential to be implemented without calibration and extensive conditioning. In this study we recorded the potential of SC K+, Na+, and H+ ISEs as a function of time following their first contact with an aqueous electrolyte solution and used these transients to determine their equilibration times. The SC electrodes were built on Au, Pt, and glassy carbon (GC) substrates using galvanostatically deposited conductive polymer (PEDOT(PSS-), poly(3,4-ethylenedioxythiophene) polystyrenesulfonate) as ion-to-electron transducer (solid internal contact) between the ion-selective membrane and the substrate. The SC electrodes built on GC and Au had significantly shorter equilibration times (between 5 and 13 min) than the SC electrodes built on Pt substrates (\u3e60 min). Such significant differences in the equilibration times of SC ISEs built on different substrate electrodes are reported here for the first time. These unexpected findings suggest that the interface between the conductive polymer and the electron-conducting substrate (EC) has significant influence on the long-term dynamic behavior of SC ISEs. (Graph Presented)

Sensorless five-phase induction motor drive with third harmonic injection and inverter output filter

The paper presents a sensorless control approach for a five-phase induction motor drive with third harmonic injection and inverter output filter. In the case of the third harmonic injection being utilised in the control, the physical machine has to be divided into two virtual machines that are controlled separately and independently. The control system structure is presented in conjunction with speed and rotor flux observers that are required for a speed sensorless implementation of the drive. The last section is dedicated to experimental results of the drive system in sensorless operation, and the uninterrupted drive operation for two open-phase faults

Innovation Technologies and Applications for Coastal Archaeological sites

Innovation Technologies and Applications for Coastal Archaeological sites project (ITACA) aims to develop and test a management system for underwater archaeological sites in coastal regions. The discovering and monitoring service will use innovative satellite remote sensing techniques combined with image processing algorithms. The project will develop a set of applications integrated in a system pursuing the following objectives: – Search and location of ancient ship wrecks; – Monitoring of ship wrecks, ruins and historical artefacts that are now submerged; – Integration of resulting search and monitoring data with on-site data into a management tool for underwater sites; – Demonstration of the system’s suitability for a service. High resolution synthetic aperture radar (TerraSAR-X, Cosmo-SkyMed) and multispectral satellite data (WorldView) will be combined to derive the relative bathymetry of the bottom of the sea up to the depth of 50 meters. The resulting data fusion will be processed using shape detection algorithms specific for archaeological items. The new algorithms, the physical modelling and the computational capabilities will be integrated into the Web-GIS, together with data recorded from surface (2D and 3D modelling) and from underwater surveys. Additional specific archaeological layers will be included into the WebGIS to facilitate the object identification through shape detection techniques and mapping. The system will be verified and validated through an extensive onground (sea) campaign carried out with both cutting edge technologies (side-scan sonar, multi beam echo sounder) and traditional means (professional scuba divers) in two test sites in Italy and Greece. The project is leaded by Planetek Hellas E.P.E. and include ALMA Sistemi sas for the “shape detection” and dissemination tasks, DHI-GRAS and Kell Srl for multispectral and SAR bathymetry. The complete consortium is composed by eleven partners and the project Kick-Off has been held in January 2014. The present contribution aims to present the project research achievements and finding at the mid-term review

Differences in Electrochemically Deposited PEDOT(PSS) Films on Au and Pt Substrate Electrodes: A Quartz Crystal Microbalance Study

Studying the responses of potassium ion-selective electrodes with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), PEDOT(PSS), as solid contact (SC) revealed significant differences in the equilibration times and standard potentials of the electrodes fabricated on Au or Pt as substrate electrodes. To trace the source of these differences, PEDOT(PSS) films were deposited under the same conditions onto Au and Pt electrodes on the surface of 10 MHz quartz crystals. During the galvanostatic polymerization, the frequency decrease of the quartz crystal was monitored by an electrochemical quartz crystal microbalance (EQCM). In the initial 15 seconds of the electrochemical deposition, the rate of PEDOT(PSS) polymer growth was significantly faster on Au compared to Pt although the current density used for the deposition was the same. Consequently, the total frequency change after a given electrolysis time was always larger on Au compared to Pt, indicating a larger deposited mass or PEDOT(PSS) layer thickness. The differences in the thicknesses of the PEDOT(PSS) films on Au and Pt could be quantitatively confirmed by X-ray photoelectron spectroscopy (XPS) etching studies. Scanning electron microscopy (SEM) analysis of PEDOT(PSS) films on Au and Pt also showed characteristic differences

Solid-Contact pH Sensor without CO2 Interference with a Superhydrophobic PEDOT-C14 as Solid Contact: The Ultimate water Layer Test

The aim of this study was to find a conducting polymer-based solid contact (SC) for ion-selective electrodes (ISEs) that could become the ultimate, generally applicable SC, which in combination with all kinds of ion-selective membranes (ISMs) would match the performance characteristics of conventional ISEs. We present data collected with electrodes utilizing PEDOT-C14, a highly hydrophobic derivative of poly(3,4-ethylenedioxythiophene), PEDOT, as SC and compare its performance characteristics with PEDOT-based SC ISEs. PEDOT-C14 has not been used in SC ISEs previously. The PEDOT-C14-based solid contact (SC) ion-selective electrodes (ISEs) (H+, K+, and Na+) have outstanding performance characteristics (theoretical response slope, short equilibration time, excellent potential stability, etc.). Most importantly, PEDOT-C14-based SC pH sensors have no CO2 interference, an essential pH sensors property when aimed for whole-blood analysis. The superhydrophobic properties (water contact angle: 136 ± 5°) of the PEDOT-C14 SC prevent the detachment of the ion-selective membrane (ISM) from its SC and the accumulation of an aqueous film between the ISM and the SC. The accumulation of an aqueous film between the ISM and its SC has a detrimental effect on the sensor performance. Although there is a test for the presence of an undesirable water layer, if the conditions for this test are not selected properly, it does not provide an unambiguous answer. On the other hand, recording the potential drifts of SC electrodes with pH-sensitive membranes in samples with different CO2 levels can effectively prove the presence or absence of a water layer in a short time period

PEDOT(PSS) as Solid Contact for Ion-Selective Electrodes: The Influence of the PEDOT(PSS) Film Thickness on the Equilibration Times

To understand the rate determining processes during the equilibration of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate-based (PEDOT(PSS)-based) solid contact (SC) ion-selective electrodes (ISEs), the surfaces of Pt, Au, and GC electrodes were coated with 0.1, 1.0, 2.0, and 4.0 µm thick galvanostatically deposited PEDOT(PSS) films. Next, potential vs time transients were recorded with these electrodes, with and without an additional potassium ion-selective membrane (ISM) coating, following their first contact with 0.1 M KCl solutions. The transients were significantly different when the multilayered sensor structures were assembled on Au or GC compared to Pt. The differences in the rate of equilibration were interpreted as a consequence of differences in the hydrophilicity of PEDOT(PSS) in contact with the substrate electrode surfaces based on X-ray photoelectron spectroscopy (XPS) and synchrotron radiation-XPS (SR-XPS) analysis of 10-100 nm thick PEDOT(PSS) films. The influence of the layer thickness of the electrochemically deposited PEDOT(PSS)-films on the hydrophilicity of these films has been documented by contact angle measurements over PEDOT(PSS)-coated Au, GC, and Pt electrode surfaces. This study demonstrates that it is possible to minimize the equilibration (conditioning) time of SC ISEs with aqueous solutions before usage by optimizing the thickness of the SC layer with a controlled ISM thickness. PEDOT(PSS)-coated Au and GC electrodes exhibit a significant negative potential drift during their equilibration in an aqueous solution. By coating the PEDOT(PSS) surface with an ISM, the negative potential drift is compensated by a positive potential drift related to the hydration of the ISM and activity changes at the PEDOT(PSS)|ISM interface. The potential drifts related to activity changes in the ISM have been determined by a novel adaptation of the "sandwich membrane" method