Determination of benzoate in cranberry and lingonberry by using a solid-contact benzoate-selective electrode.

Benzoic acid is used as a preservative in processed food, and occasionally in cosmetics and pharmaceuticals, while benzoic acid occurs naturally in, e.g., cranberry and lingonberry. Therefore, the determination of benzoate is of interest for product quality assurance, food safety, and personal health. In this work, a solid-contact benzoate-selective electrode (benzoate-ISE) was developed by utilising poly(3,4-ethylenedioxythiophene) (PEDOT) as solid contact and a solvent polymeric membrane containing a 1,3-bis(carbazolyl)urea derivative as ionophore. The benzoate-ISE was characterised in parallel with an ionophore-free control-ISE by electrochemical impedance spectroscopy and potentiometry. The presence of the ionophore in the membrane improved the selectivity to benzoate. Benzoate-ISEs and control-ISEs were used further to determine the benzoate concentration in cranberry and lingonberry by standard addition. The results obtained with both types of ISEs were compared with those obtained by ion chromatography. The results obtained with benzoate-ISEs were consistent with those obtained with ion chromatography. On the contrary, the control-ISE (without ionophore) gave significantly higher benzoate concentrations, especially in the case of cranberry where the benzoate concentration was low (ca 0.2 g kg-1) compared to lingonberry (ca 1 g kg-1). Hence, the benzoate-selectivity of the ionophore was crucial to obtain a benzoate-ISE that was practically applicable for determination of benzoate concentrations in cranberry and lingonberry.

Fast and sensitive coulometric signal transduction for ion-selective electrodes by utilizing a two-compartment cell.

Here, we propose a fast and sensitive coulometric signal transduction method for ion-selective electrodes (ISEs) by utilizing a two-compartment cell. A potassium ion-selective electrode (K+-ISE) was connected as reference electrode (RE) and placed in the sample compartment. A glassy carbon (GC) electrode coated with poly(3,4-ethylenedioxythiophene) (GC/PEDOT), or reduced graphene oxide (GC/RGO), was connected as working electrode (WE) and placed in the detection compartment together with a counter electrode (CE). The two compartments were connected with an Ag/AgCl wire. The measured cumulated charge was amplified by increasing the capacitance of the WE. The observed slope of the cumulated charge with respect to the change of the logarithm of the K+ ion activity was linearly proportional to the capacitance of the GC/PEDOT and GC/RGO, estimated from impedance spectra. Furthermore, the sensitivity of the coulometric signal transduction using a commercial K+-ISE with internal filling solution as RE and GC/RGO as WE allowed to decrease the response time while still being able to detect a 0.2% change in K+ concentration. The coulometric method utilizing a two-compartment cell was found to be feasible for the determination of K+ concentrations in serum. The advantage of this two-compartment approach, compared to the coulometric transduction described earlier, was that no current passed through the K+-ISE that was connected as RE. Therefore, current-induced polarization of the K+-ISE was avoided. Furthermore, since the GCE/PEDOT and GCE/RGO (used as WE) had a low impedance, the response time of the coulometric response decreased from minutes to seconds.

Novel Experimental Setup for Coulometric Signal Transduction of Ion-Selective Electrodes.

In this work, a novel and versatile experimental setup for coulometric signal transduction of ion-selective electrodes (ISEs) is introduced and studied. It is based on a constant potential coulometric measurement carried out using a one-compartment three-electrode electrochemical cell. In the setup, a potassium ion-selective electrode (K+- ISE) is connected as the reference electrode (RE). A poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonate (PEDOT:PSS)-based electrode with a dummy membrane (DM) and a glassy carbon (GC) rod are connected as the working electrode (WE) and counter electrode (CE), respectively. Adding a non-selective dummy membrane to the structure of the WE facilitates the regulation of the measured signal and response time. The results from electrochemical impedance spectroscopy measurements carried out on the WE showed that the time constant is profoundly influenced by the dummy membrane thickness. In addition, the redox capacitance of the PEDOT:PSS film shows a better correlation with the electrode area than the film thickness. Sequential addition/dilution experiments showed the improvement of current and cumulated charge signals in the new setup studied in this work compared to the setup used in the original coulometric signal transduction method. Both conventional ISEs and solid-contact ISEs (SCISEs) were used in this work. The results showed that the coulometric response was independent of the type of ISE used as RE, confirming the versatility of the novel set-up.

Pilot study in human healthy volunteers on the use of magnetohydrodynamics in needle-free continuous glucose monitoring.

The benefits of continuous glucose monitoring (CGM) in diabetes management are extensively documented. Yet, the broader adoption of CGM systems is limited by their cost and invasiveness. Current CGM devices, requiring implantation or the use of hypodermic needles, fail to offer a convenient solution. We have demonstrated that magnetohydrodynamics (MHD) is effective at extracting dermal interstitial fluid (ISF) containing glucose, without the use of needles. Here we present the first study of ISF sampling with MHD for glucose monitoring in humans. We conducted 10 glucose tolerance tests on 5 healthy volunteers and obtained a significant correlation between the concentration of glucose in ISF samples extracted with MHD and capillary blood glucose samples. Upon calibration and time lag removal, the data indicate a Mean Absolute Relative Difference (MARD) of 12.9% and Precision Absolute Relative Difference of 13.1%. In view of these results, we discuss the potential value and limitations of MHD in needle-free glucose monitoring.

A review on conjugated polymer-based electronic tongues.

Electronic tongues (e-tongues) are analytical technologies that mimic the biological tongues which are non-specific, low-selective, and cross-sensitive taste systems. The e-tongues consist of an array of sensors, being able to produce electrical signals that correspond to particular chemical compositions of a sample solution. The performance and efficiency of e-tongues have been optimized for many years via the development of novel materials and technologies. Various conjugated polymers (CPs) have been used in e-tongues over the past decades thanks to their fascinating electrical properties and wide-ranging chemistries. In most studies, CPs such as polypyrrole (PPy), polyaniline (PANI), polythiophene (PT), and poly(3,4-ethylenedioxythiophene) (PEDOT), have drawn considerable interest in e-tongues because of their controllable electrical properties, relatively facile and cost-effective preparation, and good environmental stability that can significantly enhance their versatility, compared to other types of e-tongues. This review article reports major conjugated polymer-based e-tongues (CPETs) that have been studied with these aforementioned CPs over the last two decades.

Long-Time Evaluation of Solid-State Composite Reference Electrodes.

In this study, the performance and long-time evaluation of solid-state composite (SSC) reference electrodes were investigated. The stability of all the SSC reference electrodes was continuously monitored by using potentiometry and electrochemical impedance spectroscopy methods over a period of several months. A multi-solution protocol was used to study the influence of the ionic strength of the sample solution, ion charge, and mobility, and the sample pH values on the performance of the reference electrodes. The SSC reference electrodes were used in the calibration of commercial indicator electrodes for different ions at different temperatures. The concentrations of K+, Na+, Ca2+, and Cl- ions and pH values were measured in river water samples at different temperatures using the SSC reference electrodes. The obtained results for the same samples were compared with the results given by an independent laboratory specialized in routine water analyses. The agreement between the results was very good and even better than the case where commercial reference electrodes were used. Our study showed that the SSC reference electrodes exhibit good long-term stability and excellent performance, both in the calibrations and analyses of environmental samples.

Influence of enzyme immobilization and skin-sensor interface on non-invasive glucose determination from interstitial fluid obtained by magnetohydrodynamic extraction.

We integrated a magnetohydrodynamic fluid extractor with an amperometric glucose biosensor to develop a wearable device for non-invasive glucose monitoring. Reproducible fluid extraction through the skin and efficient transport of the extracted fluid to the biosensor surface are prerequisites for non-invasive glucose monitoring. We optimized the enzyme immobilization and the interface layer between the sensing device and the skin. The monitoring device was evaluated by extracting fluid through porcine skin followed by glucose detection at the biosensor. The biosensor featured a screen-printed layer of Prussian Blue that was coated with a layer containing glucose oxidase. Both physical entrapment of glucose oxidase in chitosan and tethering of glucose oxidase to electrospun nanofibers were evaluated. Binding of glucose oxidase to nanofibers under mild conditions provided a stable biosensor with analytical performance suitable for accurate detection of micromolar concentrations of glucose. Hydrogels of varying thickness (95-2000 µm) as well as a thin (30 µm) nanofibrous polycaprolactone mat were studied as an interface layer between the biosensor and the skin. The effect of mass transfer phenomena at the biosensor-skin interface on the analytical performance of the biosensor was evaluated. The sensing device detected glucose extracted through porcine skin with an apparent (overall) sensitivity of -0.8 mA/(M·cm2), compared to a sensitivity of -17 mA/(M·cm2) for measurement in solution. The amperometric response of the biosensor correlated with the glucose concentration in the fluid that had been extracted through porcine skin with the magnetohydrodynamic technique.

Environmental footprint of voltammetric sensors based on screen-printed electrodes: An assessment towards "green" sensor manufacturing.

Voltammetric sensors based on screen-printed electrodes (SPEs) await diverse applications in environmental monitoring, food, agricultural and biomedical analysis. However, due to the single-use and disposable characteristics of SPEs and the scale of measurements performed, their environmental impacts should be considered. A life cycle assessment was conducted to evaluate the environmental footprint of SPEs manufactured using various substrate materials (SMs: cotton textile, HDPE plastic, Kraft paper, graphic paper, glass, and ceramic) and electrode materials (EMs: platinum, gold, silver, copper, carbon black, and carbon nanotubes (CNTs)). The greatest environmental impact was observed when cotton textile was used as SM. HDPE plastic demonstrated the least impact (13 out of 19 categories), followed by ceramic, glass and paper. However, considering the end-of-life scenarios and release of microplastics into the environment, ceramic, glass or paper could be the most suitable options for SMs. Amongst the EMs, the replacement of metals, especially noble metals, by carbon-based EMs greatly reduces the environmental footprint of SPEs. Compared with other materials, carbon black was the least impactful on the environment. On the other hand, copper and waste-derived CNTs (WCNTs) showed low impacts except for terrestrial ecotoxicity and human toxicity (non-cancer) potentials. In comparison to commercial CNTs (CCNTs), WCNTs demonstrated lower environmental footprint and comparable voltammetric performance in heavy metal detections, justifying the substitution of CCNTs with WCNTs in commercial applications. In conclusion, a combination of carbon black or WCNTs EMs with ceramic, glass or paper SMs represents the most environmentally friendly SPE configurations for voltammetric sensor arrangement.

Sampling of fluid through skin with magnetohydrodynamics for noninvasive glucose monitoring.

Out of 463 million people currently with diabetes, 232 million remain undiagnosed. Diabetes is a threat to human health, which could be mitigated via continuous self-monitoring of glucose. In addition to blood, interstitial fluid is considered to be a representative sample for glucose monitoring, which makes it highly attractive for wearable on-body sensing. However, new technologies are needed for efficient and noninvasive sampling of interstitial fluid through the skin. In this report, we introduce the use of Lorentz force and magnetohydrodynamics to noninvasively extract dermal interstitial fluid. Using porcine skin as an ex-vivo model, we demonstrate that the extraction rate of magnetohydrodynamics is superior to that of reverse iontophoresis. This work seeks to provide a safe, effective, and noninvasive sampling method to unlock the potential of wearable sensors in needle-free continuous glucose monitoring devices that can benefit people living with diabetes.

In situ catalytic reforming of plastic pyrolysis vapors using MSW incineration ashes.

The valorization of municipal solid waste incineration bottom and fly ashes (IBA and IFA) as catalysts for thermochemical plastic treatment was investigated. As-received, calcined, and Ni-loaded ashes prepared via hydrothermal synthesis were used as low-cost waste-derived catalysts for in-line upgrading of volatile products from plastic pyrolysis. It was found that both IBA and air pollution control IFA (APC) promote selective production of BTEX compounds (i.e., benzene, toluene, ethylbenzene, and xylenes) without significantly affecting the formation of other gaseous and liquid species. There was insignificant change in the product distribution when electrostatic precipitator IFA (ESP) was used, probably due to the lack of active catalytic species. Calcined APC (C-APC) demonstrated further improvement in the BTEX yield that suggested the potential to enhance the catalytic properties of ashes through pre-treatment. By comparing with the leaching limit values stated in the European Council Decision, 2003/33/EC for the acceptance of hazardous waste at landfills, all the ashes applied remained in the same category after the calcination and pyrolysis processes, except the leaching of Cl- from the ESP, which was around the borderline. Therefore, the use of ashes in catalytic reforming application do not significantly deteriorate their metal leaching behavior. Considering its superior catalytic activity towards BTEX formation, C-APC was loaded with Ni at 15 and 30 wt%. The Ni-loading favored an increase in overall oil yield, while reducing the gas yield when compared to the benchmark Ni loaded ZSM catalyst. However, Ni addition also caused the formation of more heavier hydrocarbons (C20-C35) that would require post-treatment to recover favorable products like BTEX.

Highly sensitive and stable fructose self-powered biosensor based on a self-charging biosupercapacitor.

Herein, we present an alternative approach to obtain a highly sensitive and stable self-powered biosensor that was used to detect D-fructose as proof of concept.In this platform, we perform a two-step process, viz. self-charging the biosupercapacitor for a constant time by using D-fructose as fuel and using the stored charge to realize the detection of D-fructose by performing several polarization curves at different D-fructose concentrations. The proposed BSC shows an instantaneous power density release of 17.6 mW cm-2 and 3.8 mW cm-2 in pulse mode and at constant load, respectively. Moreover, the power density achieved for the self-charging BSC in pulse mode or under constant load allows for an enhancement of the sensitivity of the device up to 10 times (3.82 ± 0.01 mW cm-2 mM-1, charging time = 70 min) compared to the BSC in continuous operation mode and 100 times compared to the normal enzymatic fuel cell. The platform can potentially be employed as a self-powered biosensor in food or biomedical applications.

Too small to matter? Physicochemical transformation and toxicity of engineered nTiO2, nSiO2, nZnO, carbon nanotubes, and nAg.

Engineered nanomaterials (ENMs) refer to a relatively novel class of materials that are increasingly prevalent in various consumer products and industrial applications - most notably for their superlative physicochemical properties when compared with conventional materials. However, consumer products inevitably degrade over the course of their lifetime, releasing ENMs into the environment. These ENMs undergo physicochemical transformations and subsequently accumulate in the environment, possibly leading to various toxic effects. As a result, a significant number of studies have focused on identifying the possible transformations and environmental risks of ENMs, with the objective of ensuring a safe and responsible application of ENMs in consumer products. This review aims to consolidate the results from previous studies related to each stage of the pathway of ENMs from being embodied in a product to disintegration/transformation in the environment. The scope of this work was defined to include the five most prevalent ENMs based on recent projected production market data, namely: nTiO2, nSiO2, nZnO, carbon nanotubes, and nAg. The review focuses on: (i) models developed to estimate environmental concentrations of ENMs; (ii) the possible physicochemical transformations; (iii) cytotoxicity and genotoxicity effects specific to each ENM selected; and (iv) a discussion to identify potential gaps in the studies conducted and recommend areas where further investigation is warranted.

Multilayer and Surface Immobilization of EDOT-Decorated Nanocapsules.

To assess the feasibility of utilizing reagent-loaded, porous polymeric nanocapsules (NCs) for chemical and biochemical sensor design, the surfaces of the NCs were decorated with 3,4-ethylenedioxythiophene (EDOT) moieties. The pores in the capsule wall allow unhindered bidirectional diffusion of molecules smaller than the programmed pore sizes, while larger molecules are either entrapped inside or blocked from entering the interior of the nanocapsules. Here, we investigate two electrochemical deposition methods to covalently attach acrylate-based porous nanocapsules with 3,4-ethylenedioxythiophene moieties on the nanocapsule surface, i.e., EDOT-decorated NCs to the surface of an existing PEDOT film: (1) galvanostatic or bilayer deposition with supporting EDOT in the deposition solution and (2) potentiostatic deposition without supporting EDOT in the deposition solution. The distribution of the covalently attached NCs in the PEDOT films was studied by variable angle FTIR-ATR and XPS depth profiling. The galvanostatic deposition of EDOT-decorated NCs over an existing PEDOT (tetrakis(pentafluorophenyl)borate) [PEDOT(TPFPhB)] film resulted in a bilayer structure, with an interface between the NC-free and NC-loaded layers, that could be traced with variable angle FTIR-ATR measurements. In contrast, the FTIR-ATR and XPS analyses of the films deposited potentiostatically from a solution without EDOT and containing only the EDOT-decorated NCs showed small amounts of NCs in the entire cross section of the films.

LogP determination for highly lipophilic hydrogen-bonding anion receptor molecules.

Lipophilicity, usually expressed as octanol-water partition coefficient (logPo/w), is an important property in biomedical research, drug design and technology. However, high logPo/w values of complex hydrogen-bonding molecules are not easy to measure or calculate. Exemplary problematic molecules are prospective active components (ionophores) of polymeric sensor membranes - the working elements of ion-selective electrodes. High lipophilicities of the membrane components are crucial for the sensor lifetime. In this work, lipophilicities of a wide range of urea-, carbazole- and indolocarbazole-based anion receptor molecules (some newly synthesized) and two common plasticizers were determined using a chromatography-based approach and/or the COSMO-RS method. Very high logPo/w values, up to around 20, i.e. far beyond directly experimentally accessible range, were obtained. The agreement between the two approaches ranged from very good to satisfactory. Based on these results, simple fragment-based equations were developed for quick lipophilicity estimation without any specialized software. Membrane-water partition coefficients for the studied compounds were modeled. Limitations and biases of the used methods are discussed.

Design, synthesis and application of carbazole macrocycles in anion sensors.

Carboxylate sensing solid-contact ion-selective electrodes (ISEs) were created to provide a proof-of-concept ISE development process covering all aspects from in silico ionophore design to functional sensor characterization. The biscarbazolylurea moiety was used to synthesize methylene-bridged macrocycles of different ring size aiming to fine tune selectivity towards different carboxylates. Cyclization was achieved with two separate strategies, using either amide synthesis to access up to -[CH2]10- macrocycles or acyl halides to access up to -[CH2]14- macrocycles. Seventy-five receptor-anion complexes were modelled and studied with COSMO-RS, in addition to all free host molecules. In order to predict initial selectivity towards carboxylates, 1H NMR relative titrations were used to quantify binding in DMSO-d 6/H2O solvent systems of two proportions - 99.5%:0.5% m/m and 90.0%:10.0% m/m, suggesting initial selectivity towards acetate. Three ionophores were selected for successful sensor prototype development and characterization. The constructed ion-selective electrodes showed higher selectivity towards benzoate than acetate, i.e., the selectivity patterns of the final sensors deviated from that predicted by the classic titration experiments. While the binding constants obtained by NMR titration in DMSO-d 6/H2O solvent systems provided important guidance for sensor development, the results obtained in this work emphasize the importance of evaluating the binding behavior of receptors in real sensor membranes.

On-line microcolumn-based dynamic leaching method for investigation of lead bioaccessibility in shooting range soils.

In this work, a miniaturized flow-through leaching test is presented for rapid screening of potential chemical extractants to explore the bioaccessibility of lead (Pb) in contaminated shooting range soils in Valkeala, Finland. The method combines the versatility of microcolumn-based extraction methods with on-line inductively coupled plasma optical emission spectrometry (ICP OES) analysis for expedient assessment of the magnitude of the bioaccessible pools and the leaching kinetics of lead from polluted soils under variable physicochemical scenarios. Acids and salt solutions were studied as potential extractants. The efficiency of the extractants relative to the initial total amount of lead in the soil sample (509 ± 21 mg/kg) were found to increase in the following order: 0.11 M acetic acid (55%) < 1 M MgCl2 (58%) < 0.1 M NH2OH·HCl (61%) < 0.1 M citric acid (93%) < 0.1 M HCl (96%). The proposed on-line microcolumn-based method was further explored for implementation of the modified BCR (now termed Standards, Measurements and Testing Programme, SM&T) sequential extraction procedure to avail the information about different fractions available in the solid sample, and validated by mass balance calculations. The equivalent sequential procedure in a batch format was then studied and compared against the on-line microcolumn extraction method. The on-line dynamic extraction system presented in this work accepts a substantial amount of sample (2.5 g) as compared to previous flow-through mini-column setups (generally accommodating < 0.25 g of sample), thus maintaining sample representativeness and fostering comprehension of the extraction patterns for non-homogenous soil materials. The use of cotton buds and Teflon membranes and holders in the microcolumn setup facilitates the repeatable flow-through leaching of trace elements and restrict formation of preferential channels. Monitoring of the leachable trace elements in real time delivers detailed insight into the ongoing extraction process and provides a time-saving assessment of potential chemical extractants.

Real-time monitoring of the dissolution of silver nanoparticles by using a solid-contact Ag+-selective electrode.

The dissolution kinetics of silver nanoparticles (Ag NPs) to Ag+ ions is a critical factor determining the toxicity of silver nanoparticles. In this work, a solid-contact Ag+-selective electrode (Ag+-ISE) is fabricated and used to monitor the dissolution of Ag NPs. Ordered mesoporous carbon is compared with disordered mesoporous carbon as the solid-contact material for the Ag+-ISE. The ordered mesoporous carbon based solid-contact Ag+-ISE shows a linear potential response in the range of 1.0 × 10-6-1.0 × 10-3 M AgNO3 with the slope of 55.6 ± 0.8 mV/dec (n = 7) and the detection limit of 10-6.8 M. The solid-contact Ag+-ISE is used to monitor the concentration changes of Ag+ during spontaneous dissolution of Ag NPs in deionized water, and the dissolution kinetics of Ag NPs is consistent with that obtained by inductively coupled plasma-mass spectrometry (ICP-MS). Stimulated dissolution of Ag NPs induced by addition of H2O2 to the Ag NP solution is also investigated by the proposed solid-contact Ag+-ISE. This work provides a fast tool for charactering the dissolution of Ag NPs to Ag+ in real time, which is important for studying the toxicology of nanoparticles.

PVC-Based Ion-Selective Electrodes with a Silicone Rubber Outer Coating with Improved Analytical Performance.

An outer layer of pure silicone rubber (SR), i.e. SR without any plasticizer, ionophore, or lipophilic anion, was applied on top of a conventional poly(vinyl chloride) (PVC) based K+-selective membrane in a solid-contact ion-selective electrode (SC-ISE). The influence of the outer SR coating on the analytical performance of the K+-ISEs was studied. The presence of the SR coating did not affect the selectivity of the SC-ISE, indicating that the plasticizer, ionophore, and lipophilic anion are spontaneously distributed from the PVC-based membrane into the SR layer. This was confirmed by electrochemical impedance spectroscopy (EIS). Interestingly, the reproducibility of the standard potential of the conditioned SC-ISE was significantly improved from E0 ± 35.3 mV to E0 ± 3.5 mV simply by adding the SR coating on top of the plasticized PVC based K+-selective membrane. Moreover, the adsorption of bovine serum albumin (BSA) was significantly reduced at the SR coated ion-selective membrane. Thus, the addition of a SR coating on a plasticized PVC ion-selective membrane seems to be a feasible method to improve the analytical performance and to reduce the biofouling of potentiometric ion sensors.

Bioimpedance Sensor Array for Long-Term Monitoring of Wound Healing from Beneath the Primary Dressings and Controlled Formation of H2O2 Using Low-Intensity Direct Current.

Chronic wounds impose a significant financial burden for the healthcare system. Currently, assessment and monitoring of hard-to-heal wounds are often based on visual means and measuring the size of the wound. The primary wound dressings must be removed before assessment can be done. We have developed a quasi-monopolar bioimpedance-measurement-based method and a measurement system to determine the status of wound healing. The objective of this study was to demonstrate that with an appropriate setup, long-term monitoring of wound healing from beneath the primary dressings is feasible. The developed multielectrode sensor array was applied on the wound area and left under the primary dressings for 142 h. The impedance of the wounds and the surrounding intact skin area was measured regularly during the study at 150 Hz, 300 Hz, 1 kHz, and 5 kHz frequencies. At the end of the follow-up period, the wound impedance had reached the impedance of the intact skin at the higher frequencies and increased significantly at the lowest frequencies. The measurement frequency affected the measurement sensitivity in wound monitoring. The skin impedance remained stable over the measurement period. The sensor array also enabled the administration of periodical low-intensity direct current (LIDC) stimulation in order to create an antimicrobial environment across the wound area via the controlled formation of hydrogen peroxide (H2O2).