Chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles: combining hydrogen bonds and anion-π interactions to achieve optimum performance.

The performance of chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso-positions. When the meso-phenyl groups are decorated with strong electron-withdrawing substituents, attractive anion-π interactions may exist between the receptor's aromatic walls and the sandwiched anion. These anion-π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p-nitro withdrawing group on each of the meso-phenyl rings, afforded sensors that display anti-Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion-specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids.

A potassium sensor based on non-covalent functionalization of multi-walled carbon nanotubes.

Non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) by a pyrene based benzo-18-crown-6 ether 1 leads to nanostructure assemblies that play both the role of an ion-to-electron transducer and a selective recognition element in solid-contact ion-selective-electrodes (SC-ISEs). The high loading capacity (36 wt%) as well as the suitable dispersion character of the MWCNT hybrid in the ion-selective membrane (ISM) confirmed the benefit of this approach over the covalent one. The sensor has been applied successfully to the detection of potassium. Nernstian response (56.9 ± 0.9 mV per decade) was obtained (10(-5) and 10(-2) M K(+)) and the selectivity pattern was not altered by the immobilization of the ionophore on the MWCNTs. Leakage of the ionophore from the polymeric matrix is therefore avoided while the sensor construction was simplified and the analytical performances were maintained.

Ion-selective electrodes using multi-walled carbon nanotubes as ion-to-electron transducers for the detection of perchlorate.

A solid contact ion-selective electrode using for the first time multi-walled carbon nanotubes (MWCNT) for the transducer material was developed for detecting perchlorate in water. To demonstrate the excellent ion-to electron transducer ability of the MWCNTs, a 15 microm thick layer of carboxylated MWCNT was deposited between an acrylic membrane selective to perchlorate ions and a glassy carbon rod used as the substrate and electrical conductor. The electrodes showed a Nernstian response of 57 mV decade(-1) (standard deviation of 3 mV decade(-1) over time and different electrodes) across a wide linear range of 10(-6) to 10(-2) M. The limit of detection was 10(-7.4) M of perchlorate. The response time was less than 10 s for activities higher than 10(-6) M and the intermediate-term potential stability shows a small drift of 0.22 mV h(-1) recorded over 5 hours. The electrode displays a selectivity comparable to liquid-contacted ISEs containing the same membrane.

An effective nanostructured assembly for ion-selective electrodes. An ionophore covalently linked to carbon nanotubes for Pb2+ determination.

We report on the synthesis of a new hybrid material, i.e. benzo-18-crown-6 covalently linked to multi-wall carbon nanotubes, and its use in solid-state ion-selective electrodes both as a receptor and an ion-to-electron transducer. This new concept leads to potentiometric sensors with extremely high selectivity.