Uncertainty in river discharge forcings and error range on nowcasting numerical simulation of salinity and seawater temperature in Ise Bay, Japan.

We estimated the error range of the simulated salinity and seawater temperature based on the uncertainty of the river discharge into Ise Bay in a nowcasting numerical simulation model. We used two methods for calculating the river discharge forcing. In the first method, precipitation was used as the input for the storage function method. In the second method, the Basin Rainfall Index was used, which is a nowcasting dataset of river discharge simulated by the Japan Meteorological Agency. The uncertainty in annual river discharge in both methods was estimated to be within ±30 %. Simulations were conducted using the hydrodynamic simulation model. Annual simulation error ranges associated with the uncertainty in river discharge for salinity and seawater temperature were estimated to be approximately ±1.2 and ±0.15 °C, respectively. We proposed a practical research procedure that can be applied to other models and the simulation of the water environment of coastal and estuary areas.

A comparative study of indentation size effect models for different materials.

The phenomenon of indentation size effect (ISE) has received great attention in aerospace, nuclear power, microelectronics and medicine. Although researchers have proposed various ISE models, these models often involve different form and number of parameters that can make our wonder which is the best in existed ISE models. Herein, three types of ISE test data, namely, normal ISE, reverse ISE and transition of normal to reverse ISE, are used to evaluate the sixteen ISE models. The comparatively study indicates that Hou-Jennet(H-J), Nix-Gao-Feng (N-G-Fs), Nix-Gao-Hausild (N-G-H), Nix-Gao-Abu Al-Rub (N-G-A) and Nix-Gao-Qius (N-G-Qs) models can accurately predict the normal ISE. The reason for this is that the friction stress that is not related to dislocation activities or the indentation size effect of plastic zone has been introduced into these models. Therefore, these two factors should be considered in future ISE models. The sixteen ISE models are originally proposed to describe the normal ISE of different materials. However, to our surprise, some of these models are able to capture the reverse ISE and the transition of normal to reverse ISE of different materials. The determination coefficients (DC) of the sixteen ISE models are also determined for different materials. For reverse ISE, the highest DC value for Ni Carbide Silicon (NiCSi), TC4 titanium alloy (TC4) and Pulsed electro-deposited Ni (PED Ni) are given by the Exponential (EXP), Nix-Gao-Feng (N-G-Fs) and Nix-Gao-Abu Al-Rub (N-G-A) models, respectively. For the transition of normal to reverse ISE, the Nix-Gao-Yuan-Chen (N-G-YC), Nix-Gao-Feng (N-G-Fs), and Nix-Gao-Hausild (N-G-H) models produce the maximum DC for ZrO2 ceramic (ZrO2), Cu single crystals (Cu) and Y2O3-ZrO2 ceramic (Y2O3-ZrO2), respectively. Moreover, the mean DC of the Nix-Gao-Feng (N-G-Fs) model is the maximum among the sixteen ISE models, followed by the Nix-Gao-Hausild (N-G-H) model, but they cannot accurately predict the reverse ISE. Therefore, the Nix-Gao-Feng (N-G-Fs) and Nix-Gao-Hausild (N-G-H) models should be further modified to accurately predict the reverse ISE.

The Establishment of a Novel In Vitro System for Culturing Cytauxzoon felis.

Cytauxzoonosis, a highly fatal tick-borne disease in domestic cats caused by Cytauxzoon felis, poses diagnostic and therapeutic challenges due to the inability to culture the parasite in vitro. This study aimed to artificially replicate C. felis infection and characterize in vitro replication kinetics. Concanavalin A-activated feline embryonal macrophages (Fcwf-4) were plated at 3-5 × 105 cells/mL and incubated with C. felis-positive blood samples from either a (1) chronically infected bobcat (Lynx rufus), (2) chronically infected domestic cat, or (3) acutely infected domestic cat with clinical signs of cytauxzoonosis. Temporal changes in parasite load were quantified by droplet digital PCR (ddPCR), and the inhibition of infection/replication was assessed using atovaquone, imidocarb dipropionate (ID), artemisinin, ponazuril, and neutralizing antibodies. Tick cell lines AAE2 and ISE6 were also tested for infection. In vitro inoculation with chronic infection led to transient replication, while acute infection resulted in sustained replication beyond 10 days post-inoculation. Atovaquone, ID, and artemisinin inhibited replication, and neutralizing antibodies prevented infection. The inoculation of tick cells in vitro indicated infection; however, parasite replication was not observed. The results of this study established an in vitro model for studying infection dynamics, assessing therapy efficacy, and testing vaccination strategies in cytauxzoonosis-infected cats.

Determination of Fluorine by Ion-Selective Electrode and High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry with Respect to Animal Feed Safety.

Fluorine, depending on its concentration and chemical form, is essential or toxic to humans and animals. Therefore, it is crucial to be able to determine it reliably. In this study, fluorine was determined in animal feed after extraction with HCl (gastric juice simulation). The standard potentiometric method with a fluoride-selective electrode (ISE) and newly developed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GFMAS) method was applied. Feed samples turned out to be a challenge for HR-CS GFMAS. Chemical interferences (formation of competing molecules, CaF, GaCl, and GaP, instead of the target GaF molecule) and spectral effects (including a phosphorous molecule spectrum and atomic lines) were identified. An additional difficulty was caused by reagent contamination with F and memory effects. Difficulties were eliminated/reduced. The quality of ISE analysis was multi-directionally verified (including comprehensive proficiency testing). A risk of inaccuracy at low F concentration, where the calibration relationship is nonlinear, was investigated. The results of both methods were consistent, which confirms the accuracy of the methods and informs that the extracted fluorine is in fluoride form. The results of extensive ISE tests conducted in Poland in 2021-2023 have shown that, in most cases, the fluoride content is significantly lower than the threshold values.

SPOOC (Sensor for Periodic Observation of Choline): An Integrated Lab-on-a-Spoon Platform for At-Home Quantification of Choline in Infant Formula.

Choline is an essential micronutrient for infants' brain development and health. To ensure that infants receive the needed daily dose of choline, the U.S. Food and Drug Administration (FDA) has set requirements for choline levels in commercialized infant formulas. Unfortunately, not all families can access well-regulated formulas, leading to potential inadequacies in choline intake. Economic constraints or difficulties in obtaining formulas, exacerbated by situations like COVID-19, prompt families to stretch formulas. Accurate measurement of choline in infant formulas becomes imperative to guarantee that infants receive the necessary nutritional support. Yet, accessible tools for this purpose are lacking. An innovative integrated sensor for the periodic observation of choline (SPOOC) designed for at-home quantification of choline in infants' formulas and milk powders is reported. This system is composed of a choline potentiometric sensor and ionic-liquid reference electrode developed on laser-induced graphene (LIG) and integrated into a spoon-like device. SPOOC includes a micro-potentiometer that conducts the measurements and transmits results wirelessly to parents' mobile devices. SPOOC demonstrated rapid and accurate assessment of choline levels directly in pre-consuming infant formulas without any sample treatment. This work empowers parents with a user-friendly tool for choline monitoring promoting informed nutritional decision-making in the care of infants.

Subolesin knockdown in tick cells provides insights into vaccine protective mechanisms.

Ticks as obligate blood-feeding arthropod vectors of pathogenic viruses, bacteria, protozoa and helminths associated with prevalent tick-borne diseases (TBDs) worldwide. These arthropods constitute the second vector after mosquitoes that transmit pathogens to humans and the first vector in domestic animals. Vaccines constitute the safest and more effective approach to control tick infestations and TBDs, but research is needed to identify new antigens and improve vaccine formulations. The tick protein Subolesin (Sub) is a well-known vaccine protective antigen with a highly conserved sequence at both gene and protein levels in the Ixodidae and among arthropods and vertebrates. In this study, transcriptomics and proteomics analyses were conducted together with graph theory data analysis in wild type and Sub knockdown (KD) tick ISE6 cells in order to identify and characterize the functional implications of Sub in tick cells. The results support a key role for Sub in the regulation of gene expression in ticks and the relevance of this antigen in vaccine development against ticks and TBDs. Proteins with differential representation in response to Sub KD provide insights into vaccine protective mechanisms and candidate tick protective antigens.

Tracking colloidal silica particles to evaluate their dispersion and interactions in concentrated suspensions under shear force applications.

This study aimed to characterize interactions within colloidal silica particles in their concentrated suspensions, using rheo-confocal measurements and imaging, followed by image analysis. We studied the effect of shear rate (0-500 s-1) and solution pH (6, 10) on the dispersion degree of colloidal silica particles via the determination and comparison of interparticle distances and their modeling. Images corresponding to different shear rates were analyzed to identify the coordinates of the particles. These coordinates were further analyzed to calculate the distance among the particles and then their surface-to-surface distance normalized by the particle diameter (H/D). It was found that the population of the particles per unit area of the image and H/D varied with increasing shear rate. The comparison between experimentally measured and theoretically calculated H/D identified that for some particles, the former was shorter than the latter, indicating the unexpected attractions among them against the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Then, the modification of previously reported equations for H/D was suggested and confirmed its validity. Assuming pair potential interaction and hydrodynamic interaction were the main non-DLVO interactions, their magnitudes were calculated and confirmed the significance of pH and shear application strength on particle dispersion/coagulation.

Near-Infrared Laser Irradiation-Modulated High-Temperature Solid-Contact Ion-Selective Electrodes: Potentiometric Detection of Ca2+ in Seawater.

The high-temperature potentiometry operated by nonisothermal heating is a promising way to break through the traditional potentiometric responses of ion-selective electrodes (ISEs) at room temperature. Herein, a locally heated strategy through near-infrared region (NIR) laser irradiation upon the photothermal mesoporous carbon material placed between the ion-selective membrane and the glassy carbon substrate is introduced to obtain the high-temperature potentiometric performance of a solid-contact Ca2+-ISE for detection of Ca2+ in seawater. Based on the light-to-heat conversion of the mesoporous carbon-based solid contact, the temperature of the solid-contact Ca2+-ISE upon continuous NIR laser irradiation can be increased from room temperature to 60-70 °C, and the slope of the electrode is promoted up to about 30% according to the thermodynamic steady-state potentiometric response. The pulsed potentiometric response of the solid-contact Ca2+-ISE upon a pulsed NIR laser irradiation of 5 s also shows a linear change as a function of Ca2+ activities, and the improved slope from 27.1 ± 0.6 to 38.1 ± 0.9 mV/dec can be obtained under dual control of the temperature of the electrode and the transient current induced by the pulsed NIR laser irradiation. As compared to the traditional potentiometric measurement under zero-current conditions at room temperature, the NIR laser-modulated high-temperature potentiometric response provides an alternative way for measurement of the solid-contact ISEs.

A simple, low cost and fast sample preparation method for fluorine determination by ISE in leguminous seeds and oilseeds.

This work presents the first report of the application of microwave-induced combustion in disposable vessels (MIC-DV) as a simple and fast sample preparation step for fluoride determination by ion-selective electrode (ISE) in leguminous seeds and oilseeds samples. Several experimental conditions of MIC-DV were evaluated, such as sample mass, absorbing solution, volume of combustion igniter, purging time with oxygen, and the use of successive combustion cycles. The accuracy of MIC-DV/ISE method was evaluated by comparing the results obtained by microwave-induced combustion and determination by ion chromatography, with agreements ranged from 94 to 106%. The method allowed to achieve relatively low limits of quantification (8.3 to 16 µg g-1) comparing to AOAC method (40 µg g-1), besides the use of small amounts of reagents, less handling of digests, making the method greener and with portable features comparing to other methods.

In Situ Drift Monitoring and Calibration of Field-Deployed Potentiometric Sensors Using Temperature Supervision.

Potentiometric ion-selective electrodes (ISEs) have broad applications in personalized healthcare, smart agriculture, oil/gas exploration, and environmental monitoring. However, high-precision potentiometric sensing is difficult with field-deployed sensors due to time-dependent voltage drift and the need for frequent calibration. In the laboratory setting, these issues are resolved by repeated calibration by measuring the voltage response at multiple standard solutions at a constant temperature. For field-deployed sensors, it is difficult to frequently interrupt operation and recalibrate with standard solutions. Moreover, the constant surrounding temperature constraint imposed by the traditional calibration process makes it unsuitable for temperature-varying field use. To address the challenges of traditional calibration for field-deployed sensors, in this study, we propose a novel in situ calibration approach in which we use natural/external temperature variation in the field to obtain the time-varying calibration parameters, without having to relocate the sensors or use any complex system. We also develop a temperature-supervised monitoring method to detect the drift of the sensor during operation. Collectively, the temperature-based drift monitoring and in situ calibration methods allow us to monitor the drift of sensors and correct them periodically to achieve high-precision sensing. We demonstrate our approach in three testbeds: (1) under controlled temperature variation in the lab, (2) under natural temperature variation in a greenhouse, and (3) in the field to monitor nitrate activity of an agricultural site. In the laboratory study, we validate that the calibration parameters of printed nitrate ISEs can be reproduced by our proposed calibration process; therefore, it can serve as an alternative to traditional calibration processes. In the greenhouse, we show the use of natural temperature variation to calibrate the sensors and detect the drift in a fixed concentration nitrate solution. Finally, we demonstrate the use of the method to monitor the nitrate activity of an agricultural field within 10% of laboratory-based measurements (i.e., a sensitivity of 0.03 mM) for a period of 22 days. The findings highlight the prospect of temperature-based calibration and drift monitoring for high-precision sensing with field-deployed ISEs.

Ion Selective Electrode (ISE) Method for Determination of Total Fluorine and Total Organic Fluorine in Packaging Substrates.

Various testing methods and techniques have been used to identify and quantify per- and polyfluoroalkyl substances (PFAS) in food packaging. A common indirect measurement of PFAS is total fluorine (TF) and total organic fluorine (TOF). These methods are critical in rapidly screening food packaging materials for the >9000 PFAS and are often globally used for regulatory limits. However, this destructive approach requires careful sample preparation, combustion, and the analysis of the solution by a fluoride-specific electrode. The method described herein is a cost-effective, rapid, quantitative, and externally validated initial screening of packaging materials for fluoro-chemistry. This study presents validated protocols for measuring TF and TOF in packaging substrates using oxygen combustion sample preparation coupled with fluoride ion-selective electrode (F-ISE); the materials and required equipment are provided, and the step-by-step procedure from sample preparation to the analysis are described, including critical steps to minimize contamination and interferences during sample preparation.

Microhardness, Indentation Size Effect and Real Hardness of Plastically Deformed Austenitic Hadfield Steel.

Microhardness testing is a widely used method for measuring the hardness property of small-scale materials. However, pronounced indentation size effect (ISE) causes uncertainties when the method is used to estimate the real hardness. In this paper, three austenitic Hadfield steel samples of different plastic straining conditions were subjected to Vickers microhardness testing, using a range of loads from 10 to 1000 g. The obtained results reveal that the origin of ISE is derived from the fact, that the indentation load P and the resultant indent diagonal d do not obey Kick's law (P = A · d2). Instead, the P and d parameters obey Meyer's power law (P = A · dn) with n < 2. The plastically strained samples showed not only significant work hardening, but also different ISE significance, as compared to the non-deformed bulk steel. After extensive assessment of several theoretical models, including the Hays-Kendall model, Li-Bradt model, Bull model and Nix-Gao model, it was found that the real hardness can be determined by Vickers microhardness indentation and subsequent analysis using the Nix-Gao model. The newly developed method was subsequently utilised in two case studies to determine the real hardness properties of sliding worn surfaces and the subsurface hardness profile.

Optimization of Castor Oil-Based Ion Selective Electrode (ISE) with Active Agent 1,10-Phenanthroline for Aqueous Pb2+ Analysis.

This research has successfully fabricated ion selective electrode (ISE) for Pb2+ using castor oil (Ricinus communis L.)-based polyurethane (PU) membrane with 1,10-phenanthroline as the active agent. The sensitivity of the Pb2+ ISE obtained is 27.25 mV/decade with a linear range of [Pb(NO3)2] of 10−10−10−5 M and a coefficient of determination (R2) of 0.959. The system response reaches stability after 25 s of measurement. The Pb2+ has a detection limit of 10−10 M and gives a stable response at pH 7−8 with a 15-day lifetime. The investigation of the selectivity of the ISE was performed using the mixed solution method with log Kij values of <1. The selectivity order of Pb2+ ISE against the foreign ions is Ag2+ > Ca2+ > K+ > Mg2+ > Cu2+ > Fe3+ > Cr3+> Zn2+ > Cd2+. The Pb2+ ISE shows acceptable reproducibility and repeatability with standard deviation values of 0.065 and 0.0079, respectively. Fourier transform infrared (FT-IR) spectra confirmed that 1,10-phenanthroline was responsible for the formation of the Pb2+ ion entrapment via complexation. Other characterizations (crystallinity, micro-surface morphology, and mechanical strength) suggest the degradation of the membrane structure integrity after the application. The analysis results of Pb levels using the Pb2+ ISE in artificial and wastewater samples were not significantly different from the atomic absorption spectroscopy (AAS) measurement.

Temperature Self-Calibration of Always-On, Field-Deployed Ion-Selective Electrodes Based on Differential Voltage Measurement.

Originally developed for use in controlled laboratory settings, potentiometric ion-selective electrode (ISE) sensors have recently been deployed for continuous, in situ measurement of analyte concentration in agricultural (e.g., nitrate), environmental (e.g., ocean acidification), industrial (e.g., wastewater), and health-care sectors (e.g., sweat sensors). However, due to uncontrolled temperature and lack of frequent calibration in these field applications, it has been difficult to achieve accuracy comparable to the laboratory setting. In this paper, we propose a novel temperature self-calibration method where the ISE sensors can serve as their own thermometer and therefore precisely measure the analyte concentration in the field condition by compensating for the temperature variations. We validate the method with controlled experiments using pH and nitrate ISEs, which use the Nernst principle for electrochemical sensing. We show that, using temperature self-calibration, pH and nitrate can be measured within 0.3% and 5% of the true concentration, respectively, under varying concentrations and temperature conditions. Moreover, we perform a field study to continuously monitor the nitrate concentration of an agricultural field over a period of 6 days. Our temperature self-calibration approach determines the nitrate concentration within 4% of the ground truth measured by laboratory-based high-precision nitrate sensors. Our approach is general and would allow battery-free temperature-corrected analyte measurement for all Nernst principle-based sensors being deployed as wearable or implantable sensors.

Electrospraying Zwitterionic Copolymers as an Effective Biofouling Control for Accurate and Continuous Monitoring of Wastewater Dynamics in a Real-Time and Long-Term Manner.

Long-term continuous monitoring (LTCM) of water quality can provide high-fidelity datasets essential for executing swift control and enhancing system efficiency. One roadblock for LTCM using solid-state ion-selective electrode (S-ISE) sensors is biofouling on the sensor surface, which perturbs analyte mass transfer and deteriorates the sensor reading accuracy. This study advanced the anti-biofouling property of S-ISE sensors through precisely coating a self-assembled channel-type zwitterionic copolymer poly(trifluoroethyl methacrylate-random-sulfobetaine methacrylate) (PTFEMA-r-SBMA) on the sensor surface using electrospray. The PTFEMA-r-SBMA membrane exhibits exceptional permeability and selectivity to primary ions in water solutions. NH4+ S-ISE sensors with this anti-fouling zwitterionic layer were examined in real wastewater for 55 days consecutively, exhibiting sensitivity close to the theoretical value (59.18 mV/dec) and long-term stability (error <4 mg/L). Furthermore, a denoising data processing algorithm (DDPA) was developed to further improve the sensor accuracy, reducing the S-ISE sensor error to only 1.2 mg/L after 50 days of real wastewater analysis. Based on the dynamic energy cost function and carbon footprint models, LTCM is expected to save 44.9% NH4+ discharge, 12.8% energy consumption, and 26.7% greenhouse emission under normal operational conditions. This study unveils an innovative LTCM methodology by integrating advanced materials (anti-fouling layer coating) with sensor data processing (DDPA).

Low-Cost Potentiometric Sensor for Chloride Measurement in Continuous Industrial Process Control.

Recently, the new updates in legislation about drinking water control and human health have increased the demand for novel electrochemical low-cost sensors, such as potentiometric ones. Nowadays, the determination of chloride ion in aqueous solutions has attracted great attention in several fields, from industrial processes to drinking water control. Indeed, chloride plays a crucial role in corrosion, also influencing the final taste of beverages, especially coffee. The main goal is to obtain devices suitable for continuous and real-time analysis. For these reasons, we investigated the possibility to develop an easy, low-cost potentiometric chloride sensor, able to perform analysis in aqueous mediums for long immersion time and reducing the need of periodic calibration. We realized a chloride ion selective electrode made of Ag/AgCl sintered pellet and we tested its response in model solutions compatible with drinking water. The sensor was able to produce a stable, reproducible, and accurate quantification of chloride in 900 s, without the need for a preliminary calibration test. This opens the route to potential applications of this sensor in continuous, in situ, and real time measurement of chloride ions in industrial processes, with a reduced need for periodic maintenance.

Measuring magnesium - Physiological, clinical and analytical perspectives.

Magnesium is the fourth most abundant cation in the human body, essential for physiological processes and is the electrolyte with levels commonly deranged in critically ill patients. These derangements of magnesium imbalance can go unnoticed and result in poor clinical outcomes, requiring both worthy attention to abnormal values and accurate tools and methods to measure magnesium reliably. At present, clinical laboratories employ various methodologies for measuring magnesium in blood and urine. This review aims to address the role of magnesium from not only physiological and pathophysiological perspectives, but importantly to review the methods for measuring magnesium with relevant analytical considerations. Given the role of magnesium and drugs for various treatments, measuring magnesium has become more relevant as drugs can lead to magnesium imbalances. Clinical manifestations and etiology of magnesium imbalance as divided into hypomagnesemia and hypermagnesemia are also reviewed.

Investigating the effects of endogenous lipaemia on the measurement of sodium by indirect ion specific electrode potentiometry.

BACKGROUND: The widely automated method using indirect ion specific electrodes (ISE) potentiometry for determination of sodium concentration is prone to interference from lipaemia. Manufacturer-specified lipaemic (L)-index cut offs may underestimate the effects of endogenous lipaemia. METHODS: We assessed the interference on sodium concentration caused by endogenous lipaemia in 32 residual samples (from 13 patients) using indirect ISE (Cobas® 8000 modular analyser with c702 module, Roche diagnostics) and direct ISE (GEM 4000 premier, Werfen) potentiometric methods. Regression analysis (linear and non-linear) was used to determine a reliable (L)-index cut off for reporting sodium concentration. RESULTS: There was a poor correlation observed between triglyceride concentration and (L)-index. There was significant negative interference caused by endogenous lipaemia within analysed samples. Non-linear regression demonstrated a negative interference of approximately 5% at an (L)-index of 250. CONCLUSION: At present, the manufacturer advises not to report sodium concentration by indirect ISE on the Cobas® 8000 modular analyser if the (L)-index is >2000. However, this has been determined by the addition of exogenous lipids (Intralipid®) and it is clear that this is not comparable to endogenous lipaemia. To ensure patient safety, clinical laboratories should consider lowering the cut off for (L)-index that they use for reporting sodium concentration.

Evidence for reduced plasmodesmata callose accumulation in Nicotiana benthamiana leaves with increased symplastic cell-to-cell communication caused by RNA processing defects of chloroplasts.

RNA processing defects in chloroplasts were previously associated with increased plasmodesmata (PD) permeability. However, the underlying mechanisms for such association are still unknown. To provide insight into this, we silenced the expression of chloroplast-located INCREASED SIZE EXCLUSION LIMIT 2 (ISE2) RNA helicase in Nicotiana benthamiana leaves and determined an increase in PD permeability which is caused by a reduction of PD callose deposition. Moreover, the silencing of two other nuclear genes encoding chloroplastic enzymes involved in RNA processing, RH3, and CLPR2, also increased PD permeability accompanied by reduced callose accumulation at PD. In addition, we quantified the plastidic hydrogen peroxide levels using the chloroplast-targeted fluorescent sensor, HyPer, in ISE2, RH3, and CLPR2 silenced N. benthamiana leaves. The levels of chloroplastic hydrogen peroxide were not correlated with the increased cell-to-cell movement of the marker protein GFP2X. We, therefore, propose that defects in chloroplast RNA metabolism mediate PD gating by suppressing PD callose deposition, and hydrogen peroxide levels in the organelles are not directly linked to this process.