Solid-Contact Potentiometric Anion Sensing Based on Classic Silver/Silver Insoluble Salts Electrodes without Ion-Selective Membrane

Current solid potentiometric ion sensors mostly rely on polymeric-membrane-based, solid-contact, ion-selective electrodes (SC-ISEs). However, anion sensing has been a challenge with respect to cations due to the rareness of anion ionophores. Classic metal/metal insoluble salt electrodes (such as Ag/AgCl) without an ion-selective membrane (ISM) offer an alternative. In this work, we first compared the two types of SC-ISEs of Cl− with/without the ISM. It is found that the ISM-free Ag/AgCl electrode discloses a comparable selectivity regarding organic chloride ionophores. Additionally, the electrode exhibits better comprehensive performances (stability, reproducibility, and anti-interference ability) than the ISM-based SC-ISE. In addition to Cl−, other Ag/AgX electrodes also work toward single and multi-valent anions sensing. Finally, a flexible Cl− sensor was fabricated for on-body monitoring the concentration of sweat Cl− to illustrate a proof-of-concept application in wearable anion sensors. This work re-emphasizes the ISM-free SC-ISEs for solid anion sensing.

Grain-boundary-rich polycrystalline monolayer WS2 film for attomolar-level Hg2+ sensors

Emerging two-dimensional (2D) layered materials have been attracting great attention as sensing materials for next-generation high-performance biological and chemical sensors. The sensor performance of 2D materials is strongly dependent on the structural defects as indispensable active sites for analyte adsorption. However, controllable defect engineering in 2D materials is still challenging. In the present work, we propose exploitation of controllably grown polycrystalline films of 2D layered materials with high-density grain boundaries (GBs) for design of ultra-sensitive ion sensors, where abundant structural defects on GBs act as favorable active sites for ion adsorption. As a proof-of-concept, our fabricated surface plasmon resonance sensors with GB-rich polycrystalline monolayer WS2 films have exhibited high selectivity and superior attomolar-level sensitivity in Hg2+ detection owing to high-density GBs. This work provides a promising avenue for design of ultra-sensitive sensors based on GB-rich 2D layered materials.

Integration of an Aerosol-Assisted Deposition Technique for the Deposition of Functional Biomaterials Applied to the Fabrication of Miniaturised Ion Sensors

Ion-selective electrodes are at the forefront of research nowadays, with applications in healthcare, agriculture and water quality analysis among others. Despite multiple attempts of miniaturization of these polyvinyl chloride (PVC) gel-based ion sensors, no ion-sensing devices with a thickness below the micrometer range, and operating using open circuit potential, have been developed so far. This work reports the causes of this thickness limitation in potassium-selective sensors. Highly homogeneous ion-sensing films were fabricated by a method based on aerosol assisted chemical vapour deposition, leading to smooth surfaces with 27 ± 11 nm of roughness. Such homogeneity allowed the systematic study of the performance and ionic diffusion properties of the sensing films at sub-micrometer scales. Sensitivities below the Nernst response were found at low thicknesses. The nature of this reduction in sensitivity was studied, and a difference in the superficial and bulk compositions of the films was measured. An optimal configuration was found at 15 µm, with a good selectivity against Na+ (KK+, Na+ = −1.8) a limit of detection in the range of 10−4 M and esponse time below 40 s. The stability of sensors was improved by the deposition of protective layers, which expanded the lifespan of the ion sensors up to 5 weeks while preserving the Nernst sensitivity.

A miniaturized sensing device with ionically imprinted nanostructured films for the ultrasensitive detection of ions

The detection of ions is essential for a wide range of applications including biomedical diagnosis, and environmental monitoring among others. However, current ion sensors are based on thick sensing films (typically 100 µm), requiring time-consuming preparations, and have a thermodynamic limit to their sensitivity of 59 mV.Log[C]-1. Such configuration hinders the development of high-performance ion sensors due to the inherent limitations of the bulk diffusion of ions inside sensors. Consequently, they cannot be applied for high-precision applications that require high sensitivity. Furthermore, the research of anion monitoring is hampered due to the limited availability of molecular receptors with acceptable performances. We overcome such limitations by using a 300 nm nanostructured sensing film based on a novel nanoporous ion imprinted core-shell silica/gold nanoparticulate sensing film. The novel sensing film was highly selective towards chloride ions when compared to other anions such as nitrate, sulphate and carbonate. Moreover, this nanostructured sensing film exhibited above 3-fold higher sensitivity (-186.4 mV.Log[C]-1) towards chloride ions when compared to commercial devices. Such breakthrough has led to the fabrication of the smallest and most sensitive reported anion sensor working on open circuit potentiometry, with an exceptional selectivity towards chloride ions.