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An overview of ionophore-based electrodes for ammonium sensing critically analyzing contributions in the last 20 years and with focus in analytical applications.

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The growth of (bio)­sensors in analytical chemistry is mainly attributable to the development of affordable, effective, portable, and user-friendly analytical tools. In the field of sensors, paper-based devices are gaining a relevant position for their outstanding features including foldability, ease of use, and instrument-free microfluidics. Herein, a multifarious use of filter paper to detect copper ions in bodily fluids is reported by exploiting this eco-friendly material to (i) synthesize AuNPs without the use of reductants and/or external stimuli, (ii) print the electrodes, (iii) load the reagents for the assay, (iv) filter the gross impurities, and (v) preconcentrate the target analyte. Copper ions were detected down to 3 ppb with a linearity up to 400 ppb in standard solutions. The applicability in biological matrices, namely, sweat and serum, was demonstrated by recovery studies and by analyzing these biofluids with the paper-based platform and the reference method (atomic absorption spectroscopy), demonstrating satisfactory accuracy of the novel eco-designed analytical tool.

In the last 10 years, paper-based electrochemical biosensors have gathered attention from the scientific community for their unique advantages and sustainability vision. The use of papers in the design the electrochemical biosensors confers to these analytical tools several interesting features such as the management of the solution flow without external equipment, the fabrication of reagent-free devices exploiting the porosity of the paper to store the reagents, and the unprecedented capability to detect the target analyte in gas phase without any sampling system. Furthermore, cost-effective fabrication using printing technologies, including wax and screen-printing, combined with the use of this eco-friendly substrate and the possibility of reducing waste management after measuring by the incineration of the sensor, designate these type of sensors as eco-designed analytical tools. Additionally, the foldability feature of the paper has been recently exploited to design and fabricate 3D multifarious biosensors, which are able to detect different target analytes by using enzymes, antibodies, DNA, molecularly imprinted polymers, and cells as biocomponents. Interestingly, the 3D structure has recently boosted the self-powered paper-based biosensors, opening new frontiers in origami devices. This review aims to give an overview of the current state origami paper-based biosensors, pointing out how the foldability of the paper allows for the development of sensitive, selective, and easy-to-use smart and sustainable analytical devices.

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Herein, we report a novel paper-based electrochemical sensor for on-site detection of sulphur mustards. This sensor was conceived combining office paper-based electrochemical sensor with choline oxidase enzyme to deliver a sustainable sensing tool. The mustard agent detection relies on the evaluation of inhibition degree of choline oxidase, which is reversibly inhibited by sulphur mustards, by measuring the enzymatic by-product HO in chronoamperometric mode. A nanocomposite constituted of Prussian Blue nanoparticles and Carbon Black was used as working electrode modifier to improve the electroanalytical performances. This bioassay was successfully applied for the measurement of a sulphur mustard, Yprite, obtaining a detection limit in the millimolar range (LOD = 0.9 mM). The developed sensor, combined with a portable and easy-to-use instrumentation, can be applied for a fast and cost-effective detection of sulphur mustards.

Cadmium and lead are highly toxic heavy metals which cause a severe worldwide pollution. In addition to the toxic effect produced by the direct exposure, they can be bioconcentrated and accumulated in living organisms, including humans. Herein, a miniaturized and disposable electrochemical sensor was improved for the simultaneous detection of cadmium and lead ions to study the bioremediation of polluted seawater in presence of the filter-feeding marine organism Styela plicata. A screen-printed electrode modified in situ with a bismuth film was selected using the anodic stripping analysis as detection technique. This sensor was coupled with a portable potentiostat and the detection of cadmium and lead ions was carried out by Square Wave Anodic Stripping Voltammetry, allowing the simultaneous detection of both heavy metals at ppb level (LOD=0.3ppb for lead, 1.5ppb for cadmium). This analytical tool was then applied to assess the bioremediation capacity of S. plicata through a bioremediation experiment, in which the organism has been exposed to seawater artificially polluted with 1000ppb of Cd and Pb. The matrix effect of both seawater and acid digested biological samples was evaluated. A bioconcentration phenomenon was observed for both heavy metals through the analysis of S. plicata tissues. In details, Pb resulted to be about 2.5 times more bioconcentrated than Cd, giving an effective bioremediation level in seawater of 13% and 40% for Cd and Pb, respectively. Thus, our results demonstrate the capability of S. plicata to bioremediate Cd and Pb polluted seawater as well as the suitability of the electrochemical sensor for contaminated marine environment monitoring and bioremediation evaluation.