Although ion-selective electrodes have been routinely used for decades now, there are still gaps in experimental evidence regarding how these sensors operate. This especially applies to the exchange of primary ions occurring for systems already containing analyte ions from the pretreatment step. Herein, for the first time, we present an insight into this process looking at the effect of altered ratios of naturally occurring analyte isotopes and achieving isotopic equilibrium. Benefiting from the same chemical properties of all isotopes of analyte ions and spatial resolution offered by laser ablation and inductively coupled plasma mass spectrometry, obtaining insights into primary ion diffusion in the preconditioned membrane is possible. For systems that have reached isotopic equilibrium in the membrane through ion exchange and between the membrane phase and the sample, quantification of primary ions in the membrane is possible using an isotope dilution approach for a heterogeneous system (membrane-liquid sample). Experimental results obtained for silver-selective membrane show that the primary ion diffusion coefficient in the preconditioned membrane is close to (6 ± 1) × 10-9 cm2/s, being somewhat lower compared to the previously reported values for other cations.  https://www.selleckchem.com/ALK.html  Diffusion of ions in the membrane is the rate limiting step in achieving isotopic exchange equilibrium between the ion-selective membrane phase and sample solution. On the contrary to previous reports, quantification of silver present in the membrane clearly shows that contact of the membrane with silver nitrate solution of concentration 10-3 M leads to pronounced accumulation of silver ions in the membrane, reaching almost 150% of ion exchanger amount. The magnitude of this effect increases for higher concentration of the electrolyte in the solution.This study is focused on identifying novel epithelial markers in circulating extracellular vesicles (EVs) through the development of a dual sandwich-type electrochemical paper-based immunosensor for Claudin 7 and CD81 determination, as well as its validation in breast cancer (BC) patients. This immunosensor allows for rapid, sensitive, and label-free detection of these two relevant BC biomarkers. Under optimum conditions, the limit of detection for Claudin 7 was 0.4 pg mL-1, with a wide linear range of 2 to 1000 pg mL-1, while for CD81, the limit of detection was 3 pg mL-1, with a wide linear range of 0.01 to 10 ng mL-1. Finally, we validated Claudin 7 and CD81 determination in EVs from 60 BC patients and 20 healthy volunteers, reporting higher diagnostic accuracy than the one observed with classical diagnostic markers. This analysis provides a low-cost, specific, versatile, and user-friendly strategy as a robust and reliable tool for early BC diagnosis.The design of nonprecious bifunctional electrocatalysts with high activity and prolonged durability in a wide pH range is essential for the development of the highly efficient, cost-effective, and simplified overall water splitting systems. Here, we report core-shell structured MXene@carbon (MX@C) nanodot hybrids with high bifunctional activity, where N-doped carbon shells are grown in a heteroepitaxial manner strongly interacting with the MXene core. The resulting MX@C nanodot hybrids show enhanced catalytic activity for electrochemical hydrogen evolution reaction (HER) in various pH media from 0 to 14. At pH 14, MX@C achieves the low onset potential of 134 mV at 10 mA/cm2 and reduced Tafel slope of 32 mV/dec due to the facilitated charge transfer along the recombination reaction. For the oxygen evolution reaction (OER), MX@C nanodots are incorporated onto the surface of molybdenum-doped bismuth vanadate (MoBiVO4) as a cocatalyst of the photoanode, thereby achieving 1.5 times higher photocurrent density than pristine MoBiVO4 at 1.23 V (vs reversible hydrogen electrode) due to the enhanced light absorption and charge transfer efficiency. The superiority of this hybrid catalyst is demonstrated implementing the solar-assisted overall water splitting cells based on the MX@C cathode and MX@C/MoBiVO4 photoanode. These cells show the enhancement of current density from 0.78 to 1.23 mA/cm2 with long-term durability over 8 h. These results are attributed to the facile surface catalytic kinetics of the chemically and electronically coupled MX@C hybrid at the heterointerface for both OER and HER.Azapeptide nitriles are postulated to reversibly covalently react with the active-site cysteine residue of cysteine proteases and form isothiosemicarbazide adducts. We investigated the interaction of azadipeptide nitriles with the cathepsin B1 drug target (SmCB1) from Schistosoma mansoni, a pathogen that causes the global neglected disease schistosomiasis. Azadipeptide nitriles were superior inhibitors of SmCB1 over their parent carba analogs. We determined the crystal structure of SmCB1 in complex with an azadipeptide nitrile and analyzed the reaction mechanism using quantum chemical calculations. The data demonstrate that azadipeptide nitriles, in contrast to their carba counterparts, undergo a change from E- to Z-configuration upon binding, which gives rise to a highly favorable energy profile of noncovalent and covalent complex formation. Finally, azadipeptide nitriles were considerably more lethal than their carba analogs against the schistosome pathogen in culture, supporting the further development of this chemotype as a treatment for schistosomiasis.Iron oxide nanoparticles (NPs) have been extensively used for both health and technological applications. The control over their morphology, crystal microstructure, and oxidation state is of great importance to optimize their final use. However, while mature in understanding, it is still far from complete. Here we report on the effect of the amount of 1,2-hexadecanediol and/or 1-octadecene in the reaction mixture on the thermal decomposition of iron(III) acetylacetonate in oleic acid for two series of iron oxide NPs with sizes ranging from 6 to 48 nm. We show that a low amount of either compound leads to both large, mixed-phase NPs composed of magnetite (Fe3O4) and wüstite (FeO) and high reaction yields. In contrast, a higher amount of either 1,2-hexadecanediol or 1-octadecene gives rise to smaller, single-phase NPs with moderate reaction yields. By infrared spectroscopy, we have elucidated the role of 1,2-hexadecanediol, which mediates the particle nucleation and growth. Finally, we have correlated the magnetic response and the structural features of the NPs for the two series of samples.