We present here a capacitive model for the coulometric signal transduction readout of solid-contact ion-selective membrane electrodes (SC-ISE) with a conducting polymer (CP) as an intermediate layer for the detection of anions. The capacitive model correlates well with experimental data obtained for chloride-selective SC-ISEs utilizing poly(3,4-ethylenedioxythiophene) (PEDOT) doped with chloride as the ion-to-electron transducer. Additionally, Prussian blue is used as a simple sodium capacitor to further demonstrate the role of the transduction layer. The influence of different thicknesses of PEDOT as a conducting polymer transducer, different thicknesses of the overlaying ion-selective membranes deposited by drop casting and spin coating, and different compositions of the chloride-selective membrane are explored. The responses are evaluated in terms of current-time, charge-time, and charge-chloride activity relationships. The utility of the sensor with coulometric readout is illustrated by the monitoring of very small concentration changes in solution.

We present here a new family of pH insensitive ion-selective optical sensors based on emulsified nanospheres containing densely functionalized 15-, 16-, 18- and 20-membered pyreneamide derivatives.

Late endosomes are a major trafficking hub in the cell at the crossroads between endocytosis, autophagy, and degradation in lysosomes. Herein is disclosed the first small molecule allowing their selective imaging and monitoring in the form of a diazaoxatriangulene fluorophore, 1a (hexadecyl side chain). The compound is prepared in three steps from a simple carbenium precursor. In nanospheres, this pH-sensitive (pKa = 7.3), photochemically stable dye fluoresces in the red part of visible light (601 and 578 nm, acid and basic forms, respectively) with a quantum yield between 14 and 16% and an excited-state lifetime of 7.7-7.8 ns. Importantly, the protonated form 1a·H(+) provokes a specific staining of late endosome compartments (pH 5.0-5.5) after 5 h of incubation with HeLa cells. Not surprisingly, this late endosome marking depends on the intra-organelle pH, and changing the nature of the lipophilic chain provokes a loss of selectivity. Interestingly, fixation of the fluorophore is readily achieved with paraformaldehyde, giving the possibility to image both live and fixed cells.

We present here for the first time an all-solid-state chronopotentiometric ion sensing system based on selective ionophores, specifically for the carbonate anion. A chronopotentiometric readout is attractive because it may allow one to obtain complementary information on the sample speciation compared to zero-current potentiometry and detect the sum of labile carbonate species instead of only ion activity. Ferrocene covalently attached to the PVC polymeric chain acts as an ion-to-electron transducer and provides the driving force to initiate the sensing process at the membrane-sample interface. The incorporation of a selective ionophore for carbonate allows one to determine this anion in a background electrolyte. Various inner electrolyte and all-solid-state-membrane configurations are explored, and localized carbonate depletion is only observed for systems that do not contain ion-exchanger additives. The square root of the transition times extracted from the inflection point of the chronopotentiograms as a function of carbonate specie concentration follows a linear relationship. The observed linear range is 0.03-0.35 mM in a pH range of 9.50-10.05. By applying the Sand equation, the diffusion coefficient of carbonate is calculated as (9.03 ± 0.91) 10(-6) cm(2) s(-1), which corresponds to the established value. The reproducibility of assessed carbonate is better than 1%. Additionally, carbonate is monitored during titrimetric analysis as a precursor to an in situ environmental determination. Based on these results, Fc-PVC membranes doped with ionophores may form the basis of a new family of passive/active all-solid-state ion selective electrodes interrogated by a current pulse.

2 GRAPHICAL ABSTRACTCartoon illustrating NaCl permeation through water nanodroplets and Cl -exchange at the membrane/sample interface, both of which create an environment to enable the formation of FeCln 3-n complexes, leading to a non-reversibility in the redox chemistry of the membrane. RESEARCH HIGHLIGHTS electrochemistry of ferrocene derivatives in polymeric membranes  role of chloride on the irreversible oxidation of ferrocene in thin film membranes  synchrotron radiation study of chloride on the ferrocene reactivity in membranes  elimination of chloride induced irreversibility of the ferrocene reaction chemistry ABSTRACTCyclic voltammetry (CV) in chloride-based aqueous electrolytes of ferrocene molecule doped thin membranes (~200 nm in thickness) on glassy carbon (GC) substrate electrodes, both plasticized poly(vinyl chloride) (PVC) and unplasticized poly(methyl methacrylate)/poly(decyl methacrylate) (PMMA-PDMA) membranes, has shown that the electrochemical oxidation behavior is irreversible due most likely to 3 degradation of ferrocene at the buried interface (GC|membrane). Furthermore, CV of the ferrocene molecules at GC electrodes in organic solvents employing chloride-based and chloride-free organic electrolytes has demonstrated that the chloride anion is inextricably linked to this irreversible ferrocene oxidation electrochemistry. Accordingly, we have explored the electrochemical oxidation mechanism of ferrocenebased redox molecules in thin film plasticized and unplasticized polymeric membrane electrodes by coupling synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) and near edge X-ray absorption fine structure (NEXAFS) with argon ion sputtering to depth profile the electrochemically oxidized thin membrane systems. With the PVC depth profiling studies, it was not possible to precisely study the influence of chloride on the ferrocene reactivity due to the high atomic ratio of chloride in the PVC membrane; however, the depth profiling results obtained with a chlorine-free polymer (PMMA-PDMA) provided irrefutable evidence for the formation of a chloride-based iron product at the GC|PMMA-PDMA interface. Finally, we have identified conditions that prevent the irreversible conversion of ferrocene by utilizing a high loading of redox active reagent and/or an ionic liquid (IL) membrane plasticizer with high ionicity that suppresses the mass transfer of chloride.