On the performance of carbon-based screen-printed electrodes for (in)organic hydroperoxides sensing in rainwater.

Hydroperoxides play important roles in atmospheric chemical processes since they act as strong oxidants. This paper details with the modification, characterization and performance of different carbon-based screen-printed electrodes to develop a sensor that allows to analyze organic and inorganic hydroperoxides in atmospheric samples. Commercial electrodes made up of graphite, graphene, carbon nanotubes and graphene oxide were electrochemically activated and subsequently modified by layer-by-layer method with a conducting polymer of azure-A and electrodeposited platinum nanoparticles. Characterization of modified electrodes was performed by FE-SEM, XPS, Raman spectroscopy, cyclic voltammetry, and impedance spectroscopy. Even though all modified carbonaceous substrates enabled the development of competitive electrochemical sensors for (in)organic hydroperoxides detection, carbon nanotubes underlying substrate exhibited the best performances in terms of sensitivity, stability, limit of detection and linear range. This amperometric sensor displayed linear responses to hydroperoxides over 0.081-450 µM with detection limits in the range of 24-558 nM and sensitivity values among 0.0628±1.6E-4 and 0.0112±0.71E-4 µA/µM for the different hydroperoxides herein studied. The developed electrochemical sensor was successfully applied to the analysis of (in)organic hydroperoxides in rainwater samples. Measurements in rainwater were performed in a city located in the East of Spain and collected at two different sites (downtown and suburban area) on two different dates (July and November 2020). The presented results demonstrated high sensitivity and selectivity for the detection of hydroperoxides among a plethora of substances naturally present in rainwater.

Computational Design of a Molecularly Imprinted Polymer for the Biomonitoring of the Organophosphorous Metabolite Chlorferron.

Coumaphos is an organophosphorus compound used as insecticide and frequently used by beekeepers for the management of parasitic mites. The most important metabolite, chlorferron (CFN), has been identified in biological samples and foodstuff. The need to quickly identify the presence of typical metabolites, as an indication of interaction with coumaphos has driven the need to produce a highly sensitive electrochemical method for chlorferron analysis, based on molecularly imprinting polymers (MIP) technology. It showed irreversible behaviour with mixed diffusion/adsorption-controlled reactions at the electrode surface. A monoelectronic mechanism of reaction for oxidation has also been suggested. The linear range observed was from 0.158 to 75 µM. Median precision in terms of %RSD around 3% was also observed. For DPV, the limit of detection (LOD) and the limit of quantitation (LOQ) for the CFN-MIP were 0.158 µM and 0.48 µM, respectively. The obtained median % recovery was around 98%. The results were also validated to reference values obtained using GC-MS. Urine and human synthetic plasma spiked with CFN were used to demonstrate the usability of the method in biological samples, showing the potential for biomonitoring. The developed imprinted sensor showed maximum signal change less than 16.8% when related metabolites or pesticide were added to the mix, suggesting high selectivity of the MIP sensor toward CFN molecules. The results from in vitro metabolism of CMP analysed also demonstrates the potential for detection and quantification of CFN in environmental samples. The newly developed CFN-MIP sensor offers similar LoDs than chromatographic methods with shorter analysis time.

Glucose Biosensor Based on Disposable Activated Carbon Electrodes Modified with Platinum Nanoparticles Electrodeposited on Poly(Azure A).

Herein, a novel electrochemical glucose biosensor based on glucose oxidase (GOx) immobilized on a surface containing platinum nanoparticles (PtNPs) electrodeposited on poly(Azure A) (PAA) previously electropolymerized on activated screen-printed carbon electrodes (GOx-PtNPs-PAA-aSPCEs) is reported. The resulting electrochemical biosensor was validated towards glucose oxidation in real samples and further electrochemical measurement associated with the generated H2O2. The electrochemical biosensor showed an excellent sensitivity (42.7 µA mM-1 cm-2), limit of detection (7.6 µM), linear range (20 µM-2.3 mM), and good selectivity towards glucose determination. Furthermore, and most importantly, the detection of glucose was performed at a low potential (0.2 V vs. Ag). The high performance of the electrochemical biosensor was explained through surface exploration using field emission SEM, XPS, and impedance measurements. The electrochemical biosensor was successfully applied to glucose quantification in several real samples (commercial juices and a plant cell culture medium), exhibiting a high accuracy when compared with a classical spectrophotometric method. This electrochemical biosensor can be easily prepared and opens up a good alternative in the development of new sensitive glucose sensors.

Non-enzymatic screen-printed sensor based on PtNPs@polyazure A for the real-time tracking of the H2O2 secreted from living plant cells.

Monitoring of hydrogen peroxide (H2O2) in living cells has high significance for understanding its functions. We herein report an enzymeless H2O2 sensor consisting of a previously activated screen-printed carbon electrode modified with Pt nanoparticles electrogenerated on a supporting conductive layer of polyazure A-dodecyl sulfate. This electrode was used to investigate the dynamic process of H2O2 release from living grapevine cells under different (a)biotic stresses. The modified surfaces were characterized by FESEM/EDX, EIS and cyclic voltammetry. Sensor analytical performance was studied in a cell culture medium under aerobic conditions, as required for cell survival. In relation to the synergistic effect between the metal nanoparticles and the conjugated polymer, this electrode showed good stability, excellent analytical performance combined with a rapid response (<2s) and limit of detection of 24.9 nM in the culture medium. The modified electrodes could fulfill the real-time measurement requirement of H2O2 release from living plant cells to the extracellular medium operating continuously, even in experiments lasting more than 12 h. Methyl jasmonate, L-methionine, clopyralid and the fungus Botrytis cinerea were the eliciting agents chosen to induce oxidative stress in the plant cells. This work demonstrates the huge potential of this sensor for the real-time tracking of the H2O2 released from living cells under different physiological conditions.

Chemometric study on the forensic discrimination of soil types using their infrared spectral characteristics.

Soil has been utilized in criminal investigations for some time because of its prevalence and transferability. It is usually the physical characteristics that are studied; however, the research carried out here aims to make use of the chemical profile of soil samples. The research we are presenting in this work used sieved (2 mm) soil samples taken from the top soil layer (about 10 cm) that were then analyzed using mid-infrared spectroscopy. The spectra obtained were pretreated and then input into two chemometric classification tools: nonlinear iterative partial least squares followed by linear discriminant analysis (NIPALS-LDA) and partial least squares discriminant analysis (PLS-DA). The models produced show that it is possible to discriminate between soil samples from different land use types and both approaches are comparable in performance. NIPALS-LDA performs much better than PLS-DA in classifying samples to location.