On the unsuspected role of multivalent metal ions on the charge storage of a metal oxide electrode in mild aqueous electrolytes.

Insertion mechanisms of multivalent ions in transition metal oxide cathodes are poorly understood and subject to controversy and debate, especially when performed in aqueous electrolytes. To address this issue, we have here investigated the reversible reduction of nanostructured amorphous TiO2 electrodes by spectroelectrochemistry in mild aqueous electrolytes containing either a multivalent metal salt as AlCl3 or a weak organic acid as acetic acid. Our results show that the reversible charge storage in TiO2 is thermodynamically and kinetically indistinguishable when carried out in either an Al3+- or acetic acid-based electrolyte, both leading under similar conditions of pH and concentrations to an almost identical maximal charge storage of ∼115 mA h g-1. These observations are in agreement with a mechanism where the inserting/deinserting cation is the proton and not the multivalent metal cation. Analysis of the data also demonstrates that the proton source is the Brønsted weak acid present in the aqueous electrolyte, i.e. either the acetic acid or the aquo metal ion complex generated from solvation of Al3+ (i.e. [Al(H2O)6]3+). Such a proton-coupled charge storage mechanism is also found to occur with other multivalent metal ions such as Zn2+ and Mn2+, albeit with a lower efficiency than Al3+, an effect we have attributed to the lower acidity of [Zn(H2O)6]2+ and [Mn(H2O)6]2+. These findings are of fundamental importance because they shed new light on previous studies assuming reversible Al3+-insertion into metal oxides, and, more generally, they highlight the unsuspected proton donor role played by multivalent metal cations commonly involved in rechargeable aqueous batteries.

Location-dependent sensing of nitric oxide and calcium ions in living rat kidney using an amperometric/potentiometric dual microsensor.

In this paper, we report the fabrication of a dual microsensor for sensing nitric oxide (NO) and calcium ions (Ca(2+)) and its application for simultaneous NO/Ca(2+) measurements in living rat kidney tissue. NO and Ca(2+) have very important physiological functions and are both intricately involved in many biological processes. The dual NO/Ca(2+) sensor is prepared based on a dual recessed electrode possessing Pt (diameter, 25 µm) and Ag (diameter, 76 µm) microdisks. The Pt disk surface (WE1) is electrodeposited with porous Pt black and then coated with fluorinated xerogel; and used for amperometric sensing of NO. The Ag disk surface (WE2) is chloridated to AgCl, followed by silanization and then Ca(2+) selective membrane loading; and used for potentiometric sensing of Ca(2+). The dual sensor exhibits high sensitivity of WE1 to NO (40.8 ± 6.5 pA µM(-1), n = 10) and reliable Nerntian response of WE2 to Ca(2+) changes (25.7 ± 0.5 mV pCa(-1), n = 10) with excellent selectivity to only NO and Ca(2+) over common interferents and reliable stability (up to ∼4 h tissue experiment). The prepared sensor is employed for real-time monitoring of the dynamic changes of NO and Ca(2+) levels of a rat kidney, which is induced by the administration of 10 mM l-N(G)-nitroarginine methyl ester (l-NAME, a NO synthase inhibitor). Due to the small sensor dimension, location-dependent analyses of NO and Ca(2+) are carried out at two different regions of a kidney (renal medulla and cortex). Higher NO and Ca(2+) levels are observed at the medulla than at the cortex. This study verifies the feasibility for real-time monitoring of intimately connected Ca(2+) and endogenous NO production; and also for localized concentration assessments of both NO and Ca(2+).