ABSTRACT
Ion-selective electrodes (ISEs) are among the most successful electrochemical sensors used in various applications because of their ability to measure electrolyte concentrations in liquids easily. It is common practice to suppress ion fluxes through the ion-sensitive membranes in ISEs because such fluxes worsen the lower limit of detection. In this study, we propose a method to detect interfering ions using this ion flux phenomenon. As a proof of principle, a flow-type Cl-ISE based on an ion exchange membrane loaded with the target ion chloride was used to acquire transient potential profiles during standstill after the introduction of liquids containing various ion species. When the target ion of the ion-sensitive membrane was measured, there was almost no change in potential over time. In contrast, when hydrophilic interfering ions were measured, the potential gradually decreased, and when hydrophobic interfering ions were measured, the potential gradually increased. The direction and intensity of these changes over time depended on the ion species and concentrations. The main reason for these potential changes is presumed to be the change in the local ionic composition of the sample near the sensing membrane due to ion exchange between the sample and membrane. This phenomenon could not be observed in a hydrophobic ion exchanger membrane doped with a quaternary ammonium salt and was characteristically observable using hydrophilic ion exchange membranes with a high charge density and a high ion diffusion rate. Finally, using a high-throughput flow-type system, we demonstrated the detection of interfering ions in solutions containing multiple ion species by using the ion flux phenomenon.
ABSTRACT
An extensive series of silyl-protected cyanoethynylethenes (CEEs) and N,N-dimethylanilino donor-substituted CEEs have been synthesized. More extended chromophores were constructed by selective silyl deprotection and subsequent oxidative acetylenic coupling. The strong electron-accepting nature of the CEEs was revealed by a combination of 13C NMR spectroscopic and electrochemistry measurements. Donor-substituted CEEs display strong intramolecular charge-transfer (CT) character, resulting in intense, bathochromically shifted CT bands in the UV/Vis spectrum. Their structural diversity establishes them as suitable models for the study of pi-conjugation and band gap tuning in strong charge-transfer chromophores. The extent of pi-conjugation in the donor-substituted CEEs was investigated by a combination of ground-state techniques, such as X-ray crystallography, electrochemistry, B3 LYP calculations, and NMR spectroscopy. The comparison of these ground-state results with the features observed in the UV/Vis spectra reveals that-contrary to expectations-more extensive pi-conjugation can lead to larger band gaps in molecules with strong donor and acceptor moieties.
ABSTRACT
Donor-substituted cyanoethynylethenes (CEEs) were synthesised, structurally characterised and investigated for their electronic and two-photon absorption properties, revealing exceptionally strong intramolecular charge-transfer interactions.
