A 'Frugal' EGFET Sensor for Waterborne H2S.

Hydrogen sulphide (H2S) is a toxic gas soluble in water, H2Saq, as a weak acid. Since H2Saq usually originates from the decomposition of faecal matter, its presence also indicates sewage dumping and possible parallel waterborne pathogens associated with sewage. We here present a low footprint ('frugal') H2Saq sensor as an accessible resource for water quality monitoring. As a sensing mechanism, we find the chemical affinity of thiols to gold (Au) translates to H2Saq. When an Au electrode is used as a control gate (CG) or floating gate (FG) electrode in the electric double layer (EDL) pool of an extended gate field effect transistor (EGFET) sensor, EGFET transfer characteristics shift along the CG voltage axis in response to H2Saq. We rationalise this by the interface potential from the adsorption of polar H2S molecules to the electrode. The sign of the shift changes between Au CG and Au FG, and cancels when both electrodes are Au. The sensor is selective for H2Saq over the components of urine, nor does urine suppress the sensor's ability to detect H2Saq. Electrodes can be recovered for repeated use by washing in 1M HCl. Quantitatively, CG voltage shift is fitted by a Langmuir-Freundlich (LF) model, supporting dipole adsorption over an ionic (Nernstian) response mechanism. We find a limit-of-detection of 14.9 nM, 100 times below potability.

Bridged EGFET Design for the Rapid Screening of Sorbents as Sensitisers in Water-Pollution Sensors.

We further simplify the most 'user-friendly' potentiometric sensor for waterborne analytes, the 'extended-gate field effect transistor' (EGFET). This is accomplished using a 'bridge' design, that links two separate water pools, a 'control gate' (CG) pool and a 'floating gate' (FG) pool, by a bridge filled with agar-agar hydrogel. We show electric communication between electrodes in the pools across the gel bridge to the gate of an LND150 FET. When loading the gel bridge with a sorbent that is known to act as a sensitiser for Cu2+ water pollution, namely, the ion exchanging zeolite 'clinoptilolite', the bridged EGFET acts as a potentiometric sensor to waterborne Cu2+. We then introduce novel sensitisers into the gel bridge, the commercially available resins PurometTM MTS9140 and MTS9200, which are sorbents for the extraction of mercury (Hg2+) pollution from water. We find a response of the bridged EGFET to Hg2+ water pollution, setting a template for the rapid screening of ion exchange resins that are readily available for a wide range of harmful (or precious) metal ions. We fit the potentiometric sensor response vs. pollutant concentration characteristics to the Langmuir-Freundlich (LF) model which is discussed in context with other ion-sensor characteristics.

Parallel Potentiometric and Capacitive Response in a Water-Gate Thin Film Transistor Biosensor at High Ionic Strength.

We show that an SnO2-based water-gate thin film transistor (WGTFT) biosensor responds to a waterborne analyte, the spike protein of the SARS-CoV-2 virus, by a parallel potentiometric and capacitive mechanism. We draw our conclusion from an analysis of transistor output characteristics, which avoids the known ambiguities of the common analysis based on transfer characteristics. Our findings contrast with reports on organic WGTFT biosensors claiming a purely capacitive response due to screening effects in high ionic strength electrolytes, but are consistent with prior work that clearly shows a potentiometric response even in strong electrolytes. We provide a detailed critique of prior WGTFT analysis and screening reasoning. Empirically, both potentiometric and capacitive responses can be modelled quantitatively by a Langmuir‒Freundlich (LF) law, which is mathematically equivalent to the Hill equation that is frequently used for biosensor response characteristics. However, potentiometric and capacitive model parameters disagree. Instead, the potentiometric response follows the Nikolsky-Eisenman law, treating the analyte 'RBD spike protein' as an ion carrying two elementary charges. These insights are uniquely possible thanks to the parallel presence of two response mechanisms, as well as their reliable delineation, as presented here.

Monitoring the lead-and-copper rule with a water-gated field effect transistor.

We use the natural zeolite clinoptilolite as the sensitive element in a plasticised PVC membrane. Separating a sample pool and a reference pool with such a membrane in water-gated SnO2 thin-film transistor (SnO2 WGTFT) leads to membrane potential, and thus transistor threshold shift in response to the common drinking water pollutants Pb2+ or Cu2+ in the sample pool. Threshold shift with ion concentration, c, follows a Langmuir-Freundlich (LF) characteristic. As the LF characteristic shows the steepest slope in the limit c → 0, this opens a window to limits-of-detection (LoDs) far below the 'action levels' of the 'lead-and-copper rule' for drinking water: Pb2+: LoD 0.9 nM vs 72 nM action level, Cu2+: LoD 14 nM vs 20.5 µM action level. LoDs are far lower than for membranes using organic macrocycles as their sensitive elements. Threshold shifts at the lead and copper action levels are more significant than shifts in response to variations in the concentration of non-toxic co-cations, and we discuss in detail how to moderate interference. The selective response to lead and copper qualifies clinoptilolite-sensitised WGTFTs as a low footprint sensor technology for monitoring the lead-and-copper rule, and to confirm the effectiveness of attempts to extract lead and copper from water.

A membrane-free cation selective water-gated transistor.

Sensors for the detection of waterborne cations are of great practical interest, and chemistry has synthesised a formidable catalogue of cation selective complexation agents ('ionophores') as selective sensitisers. Current ionophore-based sensors separate the complexation of the cation by the ionophore, and the transduction of complexation into an electrical signal, into separate components. We here unite both functions into a single, sensitised semiconducting layer of a water-gated organic thin film transistor (OTFT). The resulting OTFT transduces waterborne cations into an electrical signal with same selectivity, sensitivity, and limit of detection as established sensors at much simplified preparation and operation. This opens a new route to apply the 'ionophore' family of functional organic materials in practical cation sensors.

Precursor-route ZnO films from a mixed casting solvent for high performance aqueous electrolyte-gated transistors.

We significantly improved the performance of precursor-route semiconducting zinc oxide (ZnO) films in electrolyte-gated thin film transistors (TFTs). We find that the organic precursor to ZnO, zinc acetate (ZnAc), dissolves more readily in a 1 : 1 mixture of ethanol (EtOH) and acetone than in pure EtOH, pure acetone, or pure isopropanol. XPS and SEM characterisation show improved morphology of ZnO films converted from a mixed solvent cast ZnAc precursor compared to the EtOH cast precursor. When gated with a biocompatible electrolyte, phosphate buffered saline (PBS), ZnO thin film transistors (TFTs) derived from mixed solvent cast ZnAc give 4 times larger field effect current than similar films derived from ZnAc cast from pure EtOH. The sheet resistance at VG = VD = 1 V is 30 kΩ â–¡(-1), lower than for any organic TFT, and lower than for any electrolyte-gated ZnO TFT reported to date.

Manifold sensitivity improvement of swelling-based sensors.

The sensitivity of swelling-based gold core-organic shell nanoparticle vapor sensors is improved manifold by cooling sensors below ambient temperature. This is due to the reduced volatility of the analyte. Sensitivity to a particular analyte scales with temperature like that of analyte's saturated vapor pressure, thus allowing quantitative prediction of sensitivity enhancement. We believe our conclusions apply to all swelling-based sensors.

Water-Gated Transistor Using Ion Exchange Resin for Potentiometric Fluoride Sensing.

We introduce fluoride-selective anion exchange resin sorbents as sensitisers into membranes for water-gated field effect transistors (WGTFTs). Sorbents were prepared via metal (La or Al)-loading of a commercial macroporous aminophosphonic acid resin, PurometTM MTS9501, and were filled into a plasticised poly(vinyl chloride) (PVC) phase transfer membrane. We found a potentiometric response (membrane potential leading to WGTFT threshold shift) to fluoride following a Langmuir-Freundlich (LF) adsorption isotherm with saturated membrane potential up to ~480 mV, extremely low characteristic concentration c1/2 = 1/K, and picomolar limit of detection (LoD), even though ion exchange did not build up charge on the resin. La-loading gave a superior response compared to Al-loading. Membrane potential characteristics were distinctly different from charge accumulating sensitisers (e.g., organic macrocycles) but similar to the Cs+ (cation) selective ion-exchanging zeolite mineral 'mordenite'. We propose a mechanism for the observed threshold shift and investigate interference from co-solutes. Strong interference from carbonate was brought under control by 'diluting' metal loading in the resin. This work sets a template for future studies using an entirely new 'family' of sensitisers in applications where very low limit of detection is essential such as for ions of arsenic, mercury, copper, palladium, and gold.

Low cost, high sensitivity detection of waterborne Al3+ cations and F- anions via the fluorescence response of a morin derivative dye.

Morin dye is known as a cheap and readily available selective 'off → on' fluorescent sensitiser when immobilised in a phase transfer membrane for the detection of Al3+ ions. Here, a morin derivative, NaMSA, which readily dissolves in water with good long-term stability is used in conjunction with a fibre optic transducer with lock-in detection to detect Al3+ in drinking water below the potability limit. The combination of a water soluble dye and the fibre optic transducer require neither membrane preparation nor a fluorescence spectrometer yet still display a high figure-of- merit. The known ability to recover morin-based Al3+ cation sensors selectively by exposure to fluoride (F-) anions is further developed enabling a complementary sensing of either fluoride anions, or aluminium cations, using the same dye with a sub-micromolar limit-of-detection for both ions. The sensor performance parameters compare favourably to prior reports on both aqueous aluminium and fluoride ion sensing.

Adaptive and sensitive fibre-optic fluorimetric transducer for air- and water-borne analytes.

A sensitive fibre optic fluorescence intensity meter has been designed and built as a transducer to detect quenching of conjugated polymer fluorescence with minimum adjustment between air- and waterborne analytes. Only generic, commercially available parts including optical fibres, solvents, airbrush, standard optical and electronic parts, and a digital lock-in amplifier have been used, avoiding the need for a fluorescence spectrometer. To test the instrument, optical fibres were sensitised with the generic fluorescent poly(phenylene-vinylene) derivative MDMO-PPV and exposed to a variety of vapour pressures, and concentrations in water, of the nitroaromatic explosive 2,4 dinitrotoluene (DNT). We establish dimensionless Stern-Volmer constants (KSV) and limit-of-detection (LoD) for air- and water-borne DNT as KSV(air) = 1.4 × 107vs. KSV(water) = 5.8 × 106 and LoD(air) = 10.9 ppb and LoD(water) = 56 ppb. These LoDs compare favourably to prior reports. We consider our study of the MDMO-PPV/DNT system as a successful test of our transducer design and recommend its wider use.

'Rough guide' evanescent wave optrode for colorimetric metalloporphyrine sensors.

When films of zinc 5-(4-carboxyphenyl),10,15,20-triphenyl porphyrin (ZnTPP) are exposed to waterborne amine in pH- neutral or alkaline media, both Q- band and Soret band respond with a change of absorbance due to the donation of amine 'lone pair' electrons to the metalloprophyrin π orbital. However, this is difficult to reveal with a conventional spectrometer even under high amine concentration. We therefore introduce optical fibres coated with ZnTPP into a bespoke 'light balance' evanescent wave absorbance meter [doi:10.1016/j.snb.2016.05.065]. The light balance makes absorbance changes clearly visible under only 5µM aqueous amine, making PVC membranes redundant. We find sensitivity is higher, and limit- of- detection lower, in the Soret band rather than the Q- band, reflecting the stronger Soret band absorbance. Also, we find that sensitivity is higher, and limit- of- detection approximately two times lower, when rough rather than smooth fibres are used. We believe the rough fibre surface leads to enhanced evanescence, and therefore better overlap of the wave propagating in the fibre with the ZnTPP fibre cladding. We find a limit of detection to waterborne amines below 1µM, which compares well to other sensors for waterborne amines [Korent, S.M. et.al. Anal. Bioanal. Chem. 387 (2007) 2863-2870; Algarni, S. A. et.al. Talanta 153 (2016) 107-110]. We therefore recommend 'rough guide' evanescent wave optrodes, in combination with sensitive 'light balance' detector, to succeed membrane- embedding of colorimetric sensitisers such as metalloporphyrines.

Innate cation sensitivity in a semiconducting polymer.

Water-gated organic thin film transistors (OTFTs) using the hole transporting semiconducting polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), show an innate response of their threshold voltage to the addition of divalent metal cations to the gating water, without deliberately introducing an ion-sensitive component. A similar threshold response is shown for several divalent cations, but is absent for monovalent cations. Response is absent for transistors using the inorganic semiconductor ZnO, or the similar organic semiconductor poly(3-hexylthiophene) (rrP3HT), instead of PBTTT. We assign innate cation sensitivity to residues of the organometallic Pd(0) complex used as catalyst in PBTTT synthesis which bears strong resemblance to typical metal chelating agents. Organometallic Pd(0) residues are absent from ZnO, and also from rrP3HT which is polymerised with a different type of catalyst. However, when Pd(0) complex is deliberately added to rrP3HT casting solutions, resulting OTFTs also display threshold response to a divalent cation.

A water-gated organic thin film transistor as a sensor for water-borne amines.

The p-type semiconducting polymer Poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) displays innate sensitivity to water-borne amines. We demonstrate this with the help of water-gated PBTTT thin film transistors (TFTs). When octylamine is added to the gating water, TFTs respond with a significantly reduced saturated drain current. Underlying TFT drift is minimised by initial conditioning, and remaining drift can be accounted for by normalising current response to the current level under purge immediately before exposure. Normalised current response vs. amine concentration is reproducible between different transistors, and can be modelled by a Langmuir surface adsorption isotherm, which suggests physisorption of analyte at the PBTTT surface, rather than bulk penetration. Same PBTTT transistors do not respond to 1- octanol, confirming the specific affinity between amines and thiophene- based organic semiconductors.

A swelling-based chemiresistor for a biogenic odour.

Escherichia coli bacteria release 1-decanol as a byproduct of their metabolism. We demonstrate the detection of 1-decanol odour at a partial pressure in the order 100 ppb by the resistance change of a swelling-based sensor, consisting of Langmuir-Schäfer deposited Au core/organic ligand shell nanoparticle films. This is an exceptionally low limit of detection for swelling-based sensors, and relies firstly, in the careful matching of the CSNPs ligands to the targeted odour, and secondly, in the very low volatility of this odour. Sensor response can be substantially increased further when films are cooled below the freezing point of 1-decanol. We observe unexpected quantitative behaviour of our sensors: response is only weakly dependent on the odour's partial pressure, and scales differently with temperature than the response of other Au-CSNP odours to more volatile odours. This may be related to their unusually strong thermal resistance drift, the difficulties in delivering very low partial pressure odour atmospheres, and the proximity to the analyte's freezing point.