Correction: A submersible probe with in-line calibration and a symmetrical reference element for continuous direct nitrate concentration measurements.

Correction for 'A submersible probe with in-line calibration and a symmetrical reference element for continuous direct nitrate concentration measurements' by Tara Forrest , , 2023, , 519-530, https://doi.org/10.1039/D2EM00341D.

A submersible probe with in-line calibration and a symmetrical reference element for continuous direct nitrate concentration measurements.

Current methods to monitor nitrate levels in freshwater systems are outdated because they require expensive equipment and manpower. Punctual sampling on the field or at a fixed measuring station is still the accepted monitoring procedure and fails to provide real-time estimation of nitrate levels. Continuous information is of crucial importance to evaluate the health of natural aquatic systems, which can strongly suffer from a nitrogen imbalance.

Symmetric cell for improving solid-contact pH electrodes.

Traditional pH glass electrodes are designed in a symmetrical manner to guarantee the most reliable and reproducible potentiometric measurements possible. Solid-contact and other pH probes not based on glass membranes are desirable because they allow for new types of applications, may be mass fabricated and less prone to breakage. Unfortunately, however, they introduce electrochemical asymmetry because the reference element used in the reference electrode compartment is now different.

Unconditioned Symmetric Solid-Contact Electrodes for Potentiometric Sensing.

In potentiometric sensing, the preparation of the electrodes preceding a measurement is often the most time-consuming step. Eliminating the conditioning process can significantly speed up the preparation procedure, but it can also compromise the need for proper pre-equilibration of the membrane. We propose here a symmetric setup to address this challenge with an identical indicator and reference elements measured against each other, thereby compensating for potential drift.

Solid-Contact Potentiometric Cell with Symmetry.

By its nature, a traditional potentiometric cell composed of an Ag/AgCl-based reference electrode and a solid-contact indicating electrode is not symmetric. This results in undesirable potential drifts in response to a common perturbation such as a temperature change of the sample. We propose here an approach to restore symmetry by constructing a cell with two identical solid-contact ISEs used as reference and indicating electrodes.

Ion-to-electron capacitance of single-walled carbon nanotube layers before and after ion-selective membrane deposition.

The capacitance of the ion-to-electron transducer layer helps to maintain a high potential stability of solid-contact ion-selective electrodes (SC-ISEs), and its estimation is therefore an essential step of SC-ISE characterization. The established chronopotentiometric protocol used to evaluate the capacitance of the single-walled carbon nanotube transducer layer was revised in order to obtain more reliable and better reproducible values and also to allow capacitance to be measured before membrane deposition for electrode manufacturing quality control purposes. The capacitance values measured with the revised method increased linearly with the number of deposited carbon nanotube-based transducer layers and were also found to correlate linearly before and after ion-selective membrane deposition, with correlation slopes close to 1 for nitrate-selective electrodes, to 0.

Potentiometric Sensor Array with Multi-Nernstian Slope.

The sensitivity of potentiometric sensors functioning in equilibrium mode is limited by the value predicted according to the Nernst equation and inversely proportional to the charge in the analyte ion. Therefore, an increased ion charge results in a dramatic decrease in the sensor sensitivity. We propose an approach to allow one to increase the sensitivity of the potentiometric measurements by using a combined electrochemical cell composed of several identical ion-selective electrodes immersed into separate sample solutions of equal composition.

A Solid-State Reference Electrode Based on a Self-Referencing Pulstrode.

The design of solid-state reference electrodes without a liquid junction is important to allow miniature and cost-effective electrochemical sensors. To address this, a pulse control is proposed using an Ag/AgI element as reliable solid-state reference electrode. It involves the local release of iodide by a cathodic current that is immediately followed by an electromotive force (EMF) measurement that serves as the reference potential.

From Molecular and Emulsified Ion Sensors to Membrane Electrodes: Molecular and Mechanistic Sensor Design.

Selective molecular ion probes are often insoluble in water and require a hydrophobic solvent environment for strong and selective binding, which runs counter to the desire of utilizing them in a homogeneous solution. This Account aims to guide the reader on how such molecules, often coined ionophores, can be harnessed to design exceptionally useful optical and electrochemical sensors. We start here with some historical context on the design of such ionophores and continue with the explanation of the response mechanism of optical and potentiometric sensors and the role of combined components to build a robust ion sensor.

Electrochemically Switchable Polymeric Membrane Ion-Selective Electrodes.

We present here for the first time a solid contact ion-selective electrode suitable for the simultaneous sensing of cations (tetrabutylammonium) and anions (hexafluorophosphate), achieved by electrochemical switching. The membrane is based on a thin plasticized polyurethane membrane deposited on poly(3-octylthiophene) (POT) and contains a cation exchanger and lipophilic electrolyte (ETH 500). The cation exchanger is initially in excess; the ion-selective electrode exhibits an initial potentiometric response to cations.

An Interface Equilibria-Triggered Time-Dependent Diffusion Model of the Boundary Potential and Its Application for the Numerical Simulation of the Ion-Selective Electrode Response in Real Systems.

A simple dynamic model of the phase boundary potential of ion-selective electrodes is presented. The model is based on the calculations of the concentration profiles of the components in membrane and sample solution phases by means of the finite difference method. The fundamental idea behind the discussed model is that the concentration gradients in both membrane and sample solution phases determine only the diffusion of the components inside the corresponding phases but not the transfer across the interface.

Time-Dependent Determination of Unbiased Selectivity Coefficients of Ion-Selective Electrodes for Multivalent Ions.

A new method for the determination of unbiased low selectivity coefficients for two of the most prevalent cases of multivalent ions (z = 2, z = 1 and z = 1, z = 2) was theoretically and experimentally substantiated. The method is based on eliminating the primary ion concentration near the membrane by extrapolating the linearized time dependencies of selectivity coefficients determined by the separate solutions method (K(SSM) as a function of t or t, depending on the charge combination of the two ions, to infinite time. The applicability of the method is demonstrated for ionophore-based Mg-, Ca-, and Na-selective electrodes.

Improved separate solution method for determination of low selectivity coefficients.

Simple, fast, and theoretically substantiated experimental method for determination of improved selectivity coefficients is proposed. The method is based on the well-known fact that low selectivity coefficients determined by the separate solution method (SSM) are time-dependent and, upon our finding, this dependence is a well-defined linear function of time raised to the certain negative power. In particular, the selectivity coefficients obtained for equally charged primary and foreign ions by SSM linearly depend on time to the minus one-fourth.