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Here, we propose a printed 96-well microtiter paper-based chemosensor array device (PCSAD) to simultaneously detect metal ions for river water assessment. Colorimetric chemosensors for metal ions have been designed based on molecular self-assembly using off-the-shelf catechol dyes and a phenylboronic acid (PBA) derivative. The colorimetric self-assembled chemosensors consisting of catechol dyes and a PBA derivative on a 96-well microtiter paper substrate demonstrated various color changes according to the disassembly of the ensembles by the addition of nine types of metal ions. An in-house-made algorithm was used to automate imaging analysis and extract color intensities at seven types of color channels from a captured digital image, allowing for rapid data processing. The obtained information-rich inset data showed fingerprint-like colorimetric responses and was applied to the qualitative and quantitative pattern recognition of metal ions using chemometric techniques. The feasibility of the 96-well microtiter PCSAD for environmental assessment has been revealed by the demonstration of a spike-and-recovery test against metal ions in a river water sample.

Herein, a self-assembled colorimetric chemosensor array composed of off-the-shelf catechol dyes and a metal ion (i.e., Zn2+) has been used for the sulfur-containing amino acids (SCAAs; i.e., glutathione, glutathione disulfide, L–cysteine, DL–homocysteine, and L–cystine). The coordination binding–based chemosensor array (CBSA) fabricated by a competitive assay among SCAAs, Zn2+ ions, and catechol dyes [i.e., pyrocatechol violet (PV), bromopyrogallol red (BPR), pyrogallol red (PR), and alizarin red S (ARS)] yielded fingerprint-like colorimetric changes. We succeeded in the qualification of SCAAs based on pattern recognition [i.e., a linear discrimination analysis (LDA)] with 100% correct classification accuracy. The semiquantification of reduced/oxidized forms of SCAAs was also performed based on LDA. Furthermore, we carried out a spike test of glutathione in food samples using the proposed chemosensor array with regression analysis. It is worth mentioning that we achieved a 91–110% recovery rate in real sample tests, which confirmed the accuracy of the constructed model. Thus, this study represents a step forward in assessing food freshness based on supramolecular analytical methods.

A novel fluorescence chemosensor array composed of pyrenylboronic acid-based probes for multi- anion detection has been developed. The pyrenylboronic acid derivatives showed fluorescence quenching or enhancement due to photoinduced electron transfer originating from anion binding. The recognition ability was assessed by fluorescence titrations and electrospray ionization mass spectrometry. Because the array is constructed with cross-reactive probes, the combination of differential binding affinities for anions (i.e., fluoride, acetate, oxalate, malonate, citrate, dihydrogen phosphate, and pyrophosphate) and pattern recognitions, such as linear discriminant analysis, offered a successful simultaneous anion detection with a classification rate of 100%. Furthermore, the chemosensor array allowed for quantitative prediction of oxalate, malonate, and citrate in mixtures using a support vector machine. Importantly, the array system employs low-cost and commercially available reagents as probes. Thus, this study could lead to the development of user-friendly and high-throughput methods to detect a variety of analytes in complicated systems.

Herein, a very simple colorimetric chemosensor array is reported for saccharides (D-glucose, D-fructose, D-xylose, D-galactose, D-mannose, L-rhamnose, and N-acetyl-D-gluosamine). While various types of chemosensors for saccharides have been investigated extensively to-this-date, tremendous additional efforts are still required on a regular basis for the syntheses of new chemosensors. Complicated syntheses would be a bottleneck, given that artificial receptor-based chemosensing systems are not so popular in comparison to biomaterial-based (e.g., enzyme-based) sensing systems. Toward this end, chemosensor array systems using molecular self-assembled materials can avoid the abovementioned synthetic efforts and achieve simultaneous qualitative and quantitative detection of a number of guest saccharides. Using a practical approach, we focus on an indicator displacement assay (IDA) to fabricate a chemosensor array for colorimetric saccharide sensing. On this basis, 3-nitrophenylboronic acid (3-NPBA) spontaneously reacts with catechol dyes such as alizarin red S (ARS), bromopyrogallol red (BPR), pyrogallol red (PR), and pyrocatechol violet (PV), and yields boronate ester derivatives with color changes. The addition of saccharides into the aqueous solution of the boronate esters induces color recovery owing to the higher binding affinity of 3-NPBA for saccharides, thus resulting in the release of dyes. By employing this system, we have succeeded in discriminating saccharides qualitatively and quantitatively with a classification success rate of 100%. Most importantly, our chemosensor array has been fabricated by only mixing low cost commercially available reagents in situ, which means that complicated synthetic processes are avoided for saccharide sensing. We believe this simple colorimetric assay that uses only commercially available reagents can create new, user-friendly supramolecular sensing pathways for saccharides.