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Investigation of the dissolution media with a borescope made the precipitated particles visible while Raman spectroscopy measurements confirmed the appearance of the crystalline active pharmaceutical ingredient. To explain the micro-morphological differences, the shape and size of the prepared samples, the evaporation rate of residual solvents, and the influence of the electrostatic field during the preparation of ASDs had to be considered. This study demonstrated that the investigated factors have a great influence on the dissolution of the ASDs. Consequently, it is worth focusing on the selection of the appropriate ASD preparation method to avoid the deterioration of dissolution properties due to the presence of crystalline traces.An alternative thioesterification reaction via copper-catalyzed oxidative coupling of readily available aroylhydrazides with disulfides is developed, in which oxidative expulsion of N2 overcomes the activation barrier between the carboxylic acid derivatives and the products. The reaction produces various thioesters in good to excellent yields with good functional group tolerance. In the reaction, stable and easily available aroylhydrazides are used as acyl sources and the relatively odorless disulfides are used as S sources. Mechanistic investigations demonstrate that the reaction of copper salt and oxidant (NH4)2S2O8 allows for achievement of tandem processes, including deprotonation, free-radical-mediated denitrogenation, and C-S bond formation.The greatest challenge for lithium-sulfur (Li-S) batteries application is the development of cathode hosts to address the low conductivity, huge volume change, and shuttling effect of sulfur or lithium polysulfides (LiPs). Herein, we demonstrate a composite host to circumvent these problems by confining sub-nanometric manganous oxide clusters (MOCs) in nitrogen doped mesoporous carbon nanosheets. The atomic structure of MOCs is well-characterized and optimized via the extended X-ray absorption fine structure analysis and density functional theory (DFT) calculations. Benefiting from the unique design, the assembled Li-S battery displays remarkable electrochemical performances including a high reversible capacity (990 mAh g-1 after 100 cycles at 0.2 A g-1) and a superior cycle life (60% retention over 250 cycles at 2 A g-1). Both the experimental results and DFT calculations demonstrate that the well-dispersed MOCs could significantly promote the chemisorption of LiPs, thus greatly improving the capacity and rate performance.Understanding the phenomena that govern complex interfacial and directed assemblies is essential for both control and scale-up of particle syntheses. The present work describes an effort to understand, control, and tune the formation of protein-inorganic calcium-phosphate supraparticles that are produced at an oscillating air-water interface created by end-over-end rotation of the synthesis solution. Supraparticles were synthesized under an array of different conditions that varied reagent concentration, the presence of additives, tube size, and rotational speed. Paired with a fluid mechanics model of the end-over-end rotation and dimensional analysis, the sensitivity of the synthesis to physicochemical and mechanical parameters was determined. Surface tension and bubble formation were found to be important criteria for changing the size distribution of supraparticles. Thresholds for the values of the Froude, Iribarren, and rotational Reynolds numbers were identified for narrowing particle size distribution. These results both guide the specific protein-inorganic supraparticle synthesis described here and inform future manipulation and scale-up of other complex interfacial colloidal assemblies.Glycoclusters with three, four, and six arms of glycosyl triazoles were designed, synthesized, and characterized. The self-assembling properties of these molecules and their catalytic activity as ligands in copper-catalyzed azide and alkyne cycloaddition (CuAAC) reactions were studied. The compounds with a lower number of branches exhibit excellent gelation properties and can function as supramolecular gelators. The resulting gels were characterized using optical microcopy and atomic force microscopy. The glycoconjugates containing six branches showed significant catalytic activity for copper sulfate mediated cycloaddition reactions. In aqueous solutions, 1 mol % of glycoclusters to substrates was efficient at accelerating these reactions. Several trimeric compounds were found to be capable of forming co-gels with the catalytically active hexameric compounds. Using the organogels formed by the glycoconjugates as supramolecular catalysts, efficient catalysis was demonstrated for several CuAAC reactions. The metallogels with CuSO4 were also prepared as gel columns, which can be reused for the cycloaddition reactions several times. These include the preparation of a few glycosyl triazoles and aryl triazoles and isoxazoles. We expect that these sugar-based soft biomaterials will have applications beyond supramolecular catalysis for copper-catalyzed cycloaddition reactions. They may also be useful as ligands or gel matrixes for other metal-ion catalyzed organic reactions.Atomic-resolution electron microscopy is a crucial tool to elucidate the structure of matter. Recently, fast electron cameras have added the time domain to high-resolution imaging, allowing static images to be acquired as movies from which sample drift can later be removed computationally and enabling real-time observations of atomic-scale dynamics on the millisecond time scale. Even higher time resolution can be achieved with short electron pulses, yet their potential for atomic-resolution imaging remains unexplored. Here, we generate high-brightness microsecond electron pulses from a Schottky emitter whose current we briefly drive to near its limit. We demonstrate that drift-corrected imaging with such pulses can achieve atomic resolution in the presence of much larger amounts of drift than with a continuous electron beam. Moreover, such pulses enable atomic-resolution observations on the microsecond time scale, which we employ to elucidate the crystallization pathways of individual metal nanoparticles as well as the high-temperature transformation of perovskite nanocrystals.Structural materials with excellent mechanical properties are vitally important for architectural application. Guadecitabine However, the traditional structural materials with complex manufacturing processes cannot effectively regulate heat flow, causing a large impact on global energy consumption. Here, we processed a high-performance and inexpensive cooling structural material by bottom-up assembling delignified biomass cellulose fiber and inorganic microspheres into a 3D network bulk followed by a hot-pressing process; we constructed a cooling lignocellulosic bulk that exhibits strong mechanical strength more than eight times that of the pure wood fiber bulk and greater specific strength than the majority of structural materials. The cellulose acts as a photonic solar reflector and thermal emitter, enabling a material that can accomplish 24-h continuous cooling with an average dT of 6 and 8 °C during day and night, respectively. Combined with excellent fire-retardant and outdoor antibacterial performance, it will pave the way for the design of high-performance cooling structural materials.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. 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.