Supramolecular Chemistry Approach to the Design of a High-Resolution Sensor Array for Multianion Detection in Water

TLDR

Reliable sensing of structurally similar anions in water is difficult, and few analytical tests or sensor devices can detect multiple anions, as illustrated by the complex anionic composition of toothpaste. This study presents a method to fabricate simple colorimetric array‑based assays that enhance discriminatory capacity for multiple aqueous anions, including complex real‑life analytes. The method uses a hydrogel host that extracts target anions and removes solvate molecules, combined with supramolecular affinity studies to predesign an eight‑sensor colorimetric array that selectively detects fluoride and pyrophosphate while cross‑reacting with other anions. The eight‑sensor array quantified anions over 0.20–360 ppm (10 µM–20 mM) and successfully distinguished fluoride content and brand differences in several toothpaste samples.

Abstract

Reliable sensing of structurally similar anions in water is a difficult problem, and analytical tests and sensor devices for reliable sensing of multiple anions are very rare. This study describes a method for fabrication of simple colorimetric array-based assays for aqueous anion solutions, including complex analytes encountered in real-life applications. On the fundamental level, this method shows how the discriminatory capacity of sensor arrays utilizing pattern recognition operating in multianalyte environments may be dramatically improved by employing two key features. The synergy between the sensor and hydrogel host resembles the cooperative effects of an apoenzyme and cofactor: the host hydrogel helps extract the target anions from the bulk analyte while stripping the solvate molecules off the anions. In addition, the supramolecular studies of the affinity and selectivity of the potential sensors for target analytes allow for constructing an array predesigned for a particular analyte. To illustrate both aspects, an eight-sensor array utilizing colorimetric sensor materials showing selectivity for fluoride and pyrophosphate while displaying significant cross-reactivity for other anions such as carboxylates, phosphate, or chloride was used to differentiate between 10 anions. The quantitative analyses were also performed to show that the eight-sensor array was found to operate across 4 orders of magnitude concentrations (0.20−360 ppm; 10 μM to 20 mM). The applicability of this approach was demonstrated by analyzing several toothpaste brands. The toothpastes are complex analytes comprising both known and unknown anions in various concentrations. The fluoride-selective yet cross-reactive array is shown to utilize the fluoride content as the main differentiating factor while using the remaining anionic components for further differentiation between toothpaste brands.