A Polyvinylpyrrolidone Nanofibrous Sensor Doubly Decorated with Mesoporous Graphene to Selectively Detect Acetic Acid Vapors.

An original approach has been proposed for designing a nanofibrous (NF) layer using UV-cured polyvinylpyrrolidone (PVP) as a matrix, incorporating mesoporous graphene carbon (MGC) nanopowder both inside and outside the fibers, creating a sandwich-like structure. This architecture is intended to selectively adsorb and detect acetic acid vapors, which are known to cause health issues in exposed workers. The nanocomposite MGC-PVP-NFs layer was fabricated through electrospinning deposition onto interdigitated microelectrodes (IDEs) and stabilized under UV-light irradiation. To enhance the adhesion of MGC onto the surface of the nanocomposite polymeric fibers, the layer was dipped in a suspension of polyethyleneimine (PEI) and MGC. The resulting structure demonstrated promising electrical and sensing properties, including rapid responses, high sensitivity, good linearity, reversibility, repeatability, and selectivity towards acetic acid vapors. Initial testing was conducted in a laboratory using a bench electrometer, followed by validation in a portable sensing device based on consumer electronic components (by ARDUINO®). This portable system was designed to provide a compact, cost-effective solution with high sensing capabilities. Under room temperature and ambient air conditions, both laboratory and portable tests exhibited favorable linear responses, with detection limits of 0.16 and 1 ppm, respectively.

Development of a LoRaWAN IoT Node with Ion-Selective Electrode Soil Nitrate Sensors for Precision Agriculture.

Crop productivity is highly dependent on the availability of soluble nitrogen (N), e.g. nitrate, in soil. When N levels are low, fertilisers are applied to replenish the soil's reserves. Typically the timing of these applications is based on paper-based guidance and sensor-based measurements of canopy greenness, which provides an indirect measure of soil N status. However this approach often means that N fertiliser is applied inappropriately or too late, resulting in excess N being lost to the environment, or too little N to meet crop demand. To promote greater N use efficiency and improve agricultural sustainability, we developed an Internet of Things (IoT) approach for the real-time measurement of soil nitrate levels using ion-selective membrane sensors in combination with digital soil moisture probes. The node incorporates state-of-the-art IoT connectivity using a LoRaWAN transceiver. The sensing platform can transfer real-time data via a cloud-connected gateway for processing and storage. In summary, we present a validated soil sensor system for real-time monitoring of soil nitrate concentrations, which can support fertiliser management decisions, improve N use efficiency and reduce N losses to the environment.

Cation-Selective Actuator-Sensor Response of Microcrystalline Cellulose Multi-Walled Carbon Nanotubes of Different Electrolytes Using Propylene Carbonate Solvent.

Microcrystalline cellulose (MC) with 50 wt.% multi-walled carbon nanotube (MCNT) composites is obtained through extrusion, forming MC-MCNT fiber. In this study, we concentrate on three different electrolytes in propylene carbonate (PC) which have the same anions (TF-, trifluoro-methanesulfonate CF3SO3-) but different cations, EDMI+ (1-ethyl-2,3-dimethylimidazolium), Li+ (lithium ion), and TBA+ (tetrabutylammonium). Cyclic voltammetry and square wave potential steps, in combination with linear actuation measurements in a potential range of 0.7 V to -0.2 V, were conducted. Our goal in this work was to establish a cation-selective actuator-sensor device capable of distinguishing different cations. The linear actuation of MC-MCNT fiber had its main expansion at discharge due to the incorporation of TF- in the MC-MCNT fiber with the cations. In the following order, TBA+ > EDMI+ > Li+ had the best stress, strain, charge density, diffusion coefficients, and long-term stability. Chronopotentiometric measurements revealed that the cations in the PC solvent can be differentiated by their ion sizes. Further characterization of the MC-MCNT fiber was completed using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and FTIR and Raman spectroscopy.

Chemiresistive Sensor for Enhanced CO2 Gas Monitoring.

Carbon dioxide (CO2) gas sensing and monitoring have gained prominence for applications such as smart food packaging, environmental monitoring of greenhouse gases, and medical diagnostic tests. Although CO2 sensors based on metal oxide semiconductors are readily available, they often suffer from limitations such as high operating temperatures (>250 °C), limited response at elevated humidity levels (>60% RH), bulkiness, and limited selectivity. In this study, we designed a chemiresistive sensor for CO2 detection to overcome these problems. The sensing material of this sensor consists of a CO2 switchable polymer based on N-3-(dimethylamino)propyl methacrylamide (DMAPMAm) and methoxyethyl methacrylate (MEMA) [P(D-co-M)], and diethylamine. The designed sensor has a detection range for CO2 between 103 and 106 ppm even at high humidity levels (>80% RH), and it is capable of differentiating ammonia at low concentrations (0.1-5 ppm) from CO2. The addition of diethylamine improved sensor performance such as selectivity, response/recovery time, and long-term stability. These data demonstrate the potential of using this sensor for the detection of food spoilage.

Catechol oxidase nanozyme based colorimetric sensors array for highly selective distinction among multiple catecholamines.

In order to effectively monitor multiple catecholamine (CA) neurotransmitters with extreme similar structures, a rapid, sensitive and selective detection strategy has become an urgent problem to be solved. In this paper, a novel colorimetric sensors array based on CuNCs protected by various ligands such as tannic acid, ascorbic acid and polymethylacrylic acid (CuNCs@TA, CuNCs@AA and CuNCs@PMAA) was constructed. All of these CuNCs could mimic catechol oxidase to selective catalyze catechol-type analogues (such as CAs) to corresponding quinones along with color changes. Furthermore, experiments and theory calculations demonstrated that Cr6+-modification on the surface of CuNCs facilitated the steady-state kinetics of enzymatic activity. Based on these CuNCs as sensing probes, this sensors array can quickly detect different CAs (such as epinephrine (EP), including dopamine (DA), norepinephrine (NE) and l-dopa) with similar structures. When those analogues were added to the CuNC-based colorimetric array sensors, different absorbance changes were produced at 485 nm. Linear discriminant analysis (LDA) showed that the tri-probe colorimetric array sensors could recognize and distinguish these analogues, and corresponding binary and ternary mixtures could be well categorized. The value of Factor 1 of an array with varied CA concentrations had a good linear correlation, and the detection limit (LOD) was as low as 10-8∼10-9 mol/L. Four CA analogues in real samples were identified by CuNCs-based colorimetric array sensors. This work provides a fast and convenient experimental basis for monitoring the complex structure CAs neurotransmitters.

Monitoring microalgal growth of Chlorella minutissima with a new all solid-state contact nitrate selective sensor.

As third generation feedstock, microalgae are microorganisms that can grow only in the optimum conditions. There are parameters including the concentration of macro and microelements in nutrient solution, pH, temperature and light intensity that have significant impact on microalgal growth. In recent years, various sensing devices have been developed for sensitive measurement of these parameters during microalgal growth. In this study, a new potentiometric nitrate selective sensor was developed to indicate the nitrate uptake of microalgae and the effect of nitrate nutrient on microalgal growth, specifically, and this sensor was successfully applied to determine nitrate concentration in medium during microalgal growth. Moreover, the effects of nitrate, carbonate and phosphate concentration in the growth medium on biomass production of Chlorella minutissima were investigated by using Box-Behnken design method, and optimum conditions were determined for the highest biomass production of microalgae. As a result of the experiments, it was seen that the highest C. minutissima production was achieved using the medium consist of 2.63 g/L NaNO3 , 0.35 g/L Na2 CO3 and 0.4 g/L KH2 PO4. Statistically, it was observed that there was a proportional relationship between the microalgae production and investigated parameters such as carbon, nitrogen and phosphate amounts of culture mediums. The electrode showed a wide linear range between 1.0 × 10-1 and 5.0 × 10-5  M with a detection limit of the 5 × 10-6  M and the response time was found as 10 s. The results showed that developed nitrate selective sensor could be successfully applied for continuous measurement of nitrate in microalgal productions at reduced cost.

Air2Liquid Method for Selective, Sensitive Detection of Gas-Phase Organophosphates.

Environmental hazards typically are encountered in the gaseous phase; however, selective sensing modalities for identifying and quantitating compounds of interest in an inexpensive, pseudo-real-time format are severely lacking. Here, we present a novel proof-of-concept that combines an Air2Liquid sampler in conjunction with an oil-in-water microfluidic assay for detection of organophosphates. We believe this proof-of-concept will enable development of a new platform technology for semivolatile detection that we have demonstrated to detect 50 pmoles (2 ppb) of neurotoxic organophosphates.

Improved Chloride Ion Sensing Performance of Flexible Ag-NPs/AgCl Electrode Sensor Using Cu-BTC as an Effective Adsorption Layer.

We designed the flexible chloride ion selective sensor that directly monitors electrochemical reactions of chloride ions without using a reference electrode. A flexible polytetrafluoroethylene (PTFE) substrate was utilized to provide bendability to the fabricated sensor. As an ion selective material, Ag nanoparticles were employed on the MWCNTs loaded on the PTFE substrate. Enhanced adsorption property of the fabricated sensor toward the chloride ions was given by incorporation of hydrophilic copper benzene-1,3,5-tricarboxylate (Cu-BTC) with great flexibility and stability. Accordingly, compared to the bare sensor the sensing performance of the Cu-BTC treated Ag NPs/AgCl electrode sensor was improved by indicating the decrease in response and recovery time about 4 times. It elucidated that the Cu-BTC layer could work as an effective medium between the Ag-NPs surface and electrolyte containing chloride ions. As a result of contact angle measurement, the hydrophilicity much increased in the Cu-BTC treated sensor because the exposed surface of the sensor not treated by the Cu-BTC largely consisted of hydrophobic MWCNTs. Furthermore, the Cu-BTC layer could hold the electrolyte for effective adsorption of analytes with large specific surface area.

Screening of biologically important Zn2+ by a chemosensor with fluorescent turn on-off mechanism.

Reported herein the synthesis, characterization and biologically important zinc ion binding propensity of a weakly fluorescent chemosensor, 4-methyl-2,6-bis((E)-(2-(4-phenylthiazol-2-yl)hydrazono)methyl)phenol (1). 1H NMR spectroscopic titration experiment reveals the binding knack of 1 to the essential Zn2+. The photo-physical studies of 1 exhibit an enhancement in the fluorescence by several folds upon binding with the zinc ions attributed to PET-off process, with a binding constant value of 5.22×103M-1. 1 exhibits an excellent detection range for Zn2+ with lower detection limit value of 2.31×10-8M. The selectivity of 1 was studied with various mono and divalent metal cations and it was observed that most cations either quenches the fluorescence or remains unchanged except for Cd2+, which shows a slight enhancement in fluorescence intensity of 1. The ratiometric displacement of Cd2+ ions by Zn2+ ions shows an excellent selectivity towards in-situ detection of Zn2+ ions. Photo-physical studies also support the reversible binding of 1 to Zn2+ ions having on and off mechanism in presence of EDTA. Such recognition of the biologically important zinc ions finds potential application in live cell imaging.

Fabrication of novel coated pyrolytic graphite electrodes for the selective nano-level monitoring of Cd²âº ions in biological and environmental samples using polymeric membrane of newly synthesized macrocycle.

Novel 5-amino-1,3,4-thiadiazole-2-thiol unit based macrocyclic ionophore 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1(4,7).1(10,13)]henicosa-4(20),10(21),16(19)-triene-6,12,18-trithione (M1), was synthesized and characterized. Preliminary studies on M1 have showed that it has more the affinity toward Cd(2+) ion. Thus, the macrocyclic ionophore (M1) was used as electroactive material in the fabrication of PVC-membrane electrodes such as polymeric membrane electrode (PME), coated graphite electrode (CGE) and coated pyrolytic graphite electrode (CPGE) were prepared and its performance characteristic were compared with. The electroanalytical studies performed on PME, CGE and CPGE revealed that CPGE having membrane composition M1:PVC:1-CN:NaTPB in the ratio of 7:37:54:2 exhibits the best potentiometric characteristics in terms of detection limit of 7.58×10(-9) mol L(-1), Nernstian slope of 29.6 mV decade(-1) of activity. The sensor was found to be independent of pH in the range 2.5-8.5. The sensor showed a fast response time of 10s and could be used over a period of 4 months without any significant divergence in its potentiometric characteristics. The sensor has been employed for monitoring of the Cd(2+) ion in real samples and also used as an indicator electrode in the potentiometric titration of Cd(2+) ion with EDTA.

Nano-level monitoring of Mn(2+) ion by fabrication of coated pyrolytic graphite electrode based on isonicotinohydrazide derivatives.

The two ionophores N'(N',N‴E,N',N‴E)-N',N‴-((((oxybis(ethane-2,1-diyl))bis(oxy)) bis(2,1-phenylene))bis(methanylylidene))di(isonicotinohydrazide) (I1) and (N',N‴E,N',N‴E)-N',N‴-(((propane-1,3-diylbis(oxy))bis(2,1-phenylene))bis(methanylylidene))di(isonicotinohydrazide) (I2) were synthesised and investigated as neutral carrier in the fabrication of Mn(2+) ion selective sensor. Several membranes were prepared by incorporating different plasticizers and anionic excluders and their effect on potentiometric response was studied. The best analytical performance was obtained with the electrode having a membrane of composition of I2: PVC: o-NPOE: NaTPB in the ratio of 6:34:58:2 (w/w, mg). Comparative studies of coated graphite electrode (CGE) and coated pyrolytic graphite electrode (CPGE) based on I2 reveal the superiority of CPGE. The CPGE exhibits wide working concentration range of 1.23×10(-8)-1.0×10(-1) mol L(-1) and a detection limit down to 4.78×10(-9) mol L(-1) with a Nernstian slope of 29.5±0.4 mV decade(-1) of activity. The sensor performs satisfactorily over a wide pH range (3.5-9.0) and exhibited a quick response time (9s). The sensor can work satisfactorily in water-acetonitrile and water-methanol mixtures. It can tolerate 30% acetonitrile and 20% methanol content in the mixtures. The sensor could be used for a period of four months without any significant divergence in performance. The sensor reflects its utility in the quantification of Mn(2+) ion in real samples and has been successfully employed as an indicator electrode in the potentiometric titration of Mn(2+) ion with ethylenediaminetetraacetic acid (EDTA).

Fabrication of a highly selective cadmium (II) sensor based on 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane as a supramolecular ionophore.

A new cadmium (II) ion selective sensor based on 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix5) as a supramolecular carrier has been developed. The membrane solutions containing polyvinyl chloride (PVC), plasticizer, sodium tetraphenylborate (NaTPB) as a lipophilic ionic additive and kryptofix5 as an ionophore were directly coated on the surface of graphite rods. The best composition of the coated membrane (w/w%) was found to be: 30.0% PVC, 61.0% dioctyl sebacate (DOS), 6.0% NaTPB and 3.0% kryptofix5. The sensor indicates a good linear response for Cd(2+) cation over a wide concentration range from 1.0×10(-5) to 1.0×10(-1) M with a Nernstian slope of 29.8±0.1 mV/decade and the detection limit is 8.4×10(-6) M. The response time of the sensor is 15s and it can be used for 7 weeks without significant drift in potential. The sensor operates in the wide pH range of 1.0-6.0. This sensor reveals a very good selectivity toward Cd(2+) ion over a wide range of alkali, transition and heavy metal cations. The sensor was used as an indicator electrode for potentiometric titration of Cd(2+) using sodium fluoride and ethylenediaminetetraacetic acid (EDTA) solutions with a sharp potential change that occurred at the end point. In addition, the proposed sensor was successfully used for determination of Cd(2+) cation in real water samples.