The Water Uptake of Plasticized Poly(vinyl chloride) Solid‐Contact Calcium‐Selective Electrodes

A hyphenated method based on FTIR‐ATR and electrochemical impedance spectroscopy has been applied to simultaneously measure the water uptake, changes in the bulk resistance and potential of plasticized poly(vinyl chloride) (PVC) based Ca 2+ ‐selective coated‐wire (CaCWE) and solid‐contact electrodes (CaSCISEs). Most of the water uptake of the ion‐selective membranes (ISMs) used in both electrode types took place within the first 9 h in 10 −3  M CaCl 2 showing good correlation with the stabilization of the individual electrode potentials. The bulk resistance of the ISMs of the CaCWEs and the CaSCISEs with poly(3‐octylthiophene) (POT) as the solid‐contact (SC) increased most during the first 18 h in 10 −3  M CaCl 2 . The increase in the resistance was found to be related to the exchange of K + for Ca 2+ in the ISM and the formation of the Ca 2+ ‐ionophore (ETH 5234) complex having a lower diffusivity than the free K + ions. In contrary to previously published results on silicone rubber based SCISEs and poly(methyl methacrylate):poly( n ‐decyl methacrylate) membranes containing POT, the plasticized PVC‐based CaSCISEs with POT as the SC had a higher water uptake than the CaCWEs. The CaSCISEs had a detection limit of 2×10 −8  M Ca 2+ and a good potential reproducibility of 148.9±1.0 mV in 10 −4  M CaCl 2 .Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/86920/1/2156_ftp.pd

Nanoscale Potentiometry

Potentiometric sensors share unique characteristics that set them apart from other electrochemical sensors. Potentiometric nanoelectrodes have been reported and successfully used for many decades, and we review these developments. Current research chiefly focuses on nanoscale films at the outer or the inner side of the membrane, with outer layers for increasing biocompatibility, expanding the sensor response, or improving the limit of detection (LOD). Inner layers are mainly used for stabilizing the response and eliminating inner aqueous contacts or undesired nanoscale layers of water. We also discuss the ultimate detectability of ions with such sensors and the power of coupling the ultra-low LODs of ion-selective electrodes with nanoparticle labels to give attractive bioassays that can compete with state-of-the-art electrochemical detection

Solid-state reference electrodes based on carbon nanotubes and polyacrylate membranes

A novel potentiometric solid-state reference electrode containing single-walled carbon nanotubes as the transducer layer between a polyacrylate membrane and the conductor is reported here. Single-walled carbon nanotubes act as an efficient transducer of the constant potentiometric signal originating from the reference membrane containing the Ag/AgCl/Cl− ions system, and they are needed to obtain a stable reference potentiometric signal. Furthermore, we have taken advantage of the light insensitivity of single-walled carbon nanotubes to improve the analytical performance characteristics of previously reported solid-state reference electrodes. Four different polyacrylate polymers have been selected in order to identify the most efficient reservoir for the Ag/AgCl system. Finally, two different arrangements have been assessed: (1) a solid-state reference electrode using photo-polymerised n-butyl acrylate polymer and (2) a thermo-polymerised methyl methacrylate:n-butyl acrylate (1:10) polymer. The sensitivity to various salts, pH and light, as well as time of response and stability, has been tested: the best results were obtained using single-walled carbon nanotubes and photo-polymerised n-butyl acrylate polymer. Water transport plays an important role in the potentiometric performance of acrylate membranes, so a new screening test method has been developed to qualitatively assess the difference in water percolation between the polyacrylic membranes studied. The results presented here open the way for the true miniaturisation of potentiometric systems using the excellent properties of single-walled carbon nanotubes