Oxyethylene chain-cation complexation: nonionic polyoxyethylene detergents attain a positive charge and demonstrate electrostatic head group interactions.

We report literature data indicating that the polyoxyethylene chain of polyoxyethylene detergents attracts cations via dipole-ion interactions thereby attaining a positive charge character. This implies that nonionic polyoxyethylene detergents like Triton X-100 and C12E8 may interact electrostatically with phospholipid head groups. We describe how a positive charge character of Triton X-100 and C12E8 can explain their hitherto mysterious stomatocytogenic shape altering effect in human erythrocytes.

Potential Stability of All-Solid-State Ion-Selective Electrodes Using Conducting Polymers as Ion-to-Electron Transducers.

Demanding analytical applications such as on-line process analysis and clinical analysis require robust, reliable, and maintenance-free ion sensors of high potential stability. In this work the stability of the electrode potential of all-solid-state ion-selective electrodes using conducting polymers as ion-to-electron transducers is critically evaluated by using chronopotentiometry and electrochemical impedance spectroscopy. This study is focused on the relationship between the potential stability of the electrode and the capacitance of the solid contact where ion-to-electron transduction takes place. The influence of this capacitance on the potential stability of all-solid-state ion-selective electrodes is studied experimentally by using conducting polymer layers of different thickness as solid contacts in potassium ion-selective electrodes based on a solvent polymeric membrane. Because of its excellent environmental stability, the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is used as a model compound for the solid contact material. Chronopotentiometry is found to be a convenient and fast experimental method to critically evaluate the potential stability of different types of ion-selective electrodes.

Potentiometric response of poly(3-octylthiophene), poly(3-methylthiophene) and polythiophene in aqueous solutions.

The potentiometric response of some polythiophenes in aqueous solutions has been investigated. Polythiophene (PT), poly(2,2'-bithiophene) (PBT), poly(3-methylthiophene) (PMT), poly(3-octylthiophene) (POT) and poly(4,4'-dioctyl2,2'-bithiophene) (POTd) were electrochemically deposited on platinum in 0.1M LiBF(4)-propylene carbonate solution containing the corresponding monomer or dimer. Polymer electrodes were also prepared by solution casting of chemically synthesized poly(3-octylthiophene) (POTc) dissolved in chloroform. After film deposition (electrochemical or chemical) the polymer coated electrodes were used as indicator electrodes in potentiometric measurements. The open-circuit potential of the polymer electrodes was measured in aqueous solutions containing inorganic salts (10(-1)-10(-4)M). Interestingly, all the polythiophenes studied were found to give a cationic response to monovalent cations such as H(+), Li(+), Na(+), K(+) and NH(+)(4) (Cl(-) salts). The slope, calculated from the linear part of the response curve, was found to depend on the polythiophene used but always remained lower than that predicted for a Nernstian response. The polythiophenes also showed some sensitivity to divalent cations such as Mg(2+) and Ca(2+) (Cl(-)-salts). POT was used as the polymer to study the influence of the polymerization conditions on the potentiometric response. By investigating different polymers from the polythiophene family it was possible to evaluate how the starting material (monomer or dimer) and the presence of alkyl side-chains influence the potentiometric response of the polymer membranes.

Studies of the mechanically generated noise in static mercury drop electrodes.

The moving parts needed for the operation of a mechanized static mercury drop electrode were found to generate additional noise which affects measurement of the polarographic current. A Fourier transformation method was employed in analysis of experimental data giving information about the frequency, amplitude and decay characteristics of the noise. The dominant noise frequency was found to depend on the drop size. Drop formation at a potential where no electrolysis takes place combined with a waiting period long enough for the mechanical vibrations to decay improved the precision of the polarographic current measurement.