Sol-Gel Synthesis of Ceria-Zirconia-Based High-Entropy Oxides as High-Promotion Catalysts for the Synthesis of 1,2-Diketones from Aldehyde.

Efficient Lewis-acid-catalyzed direct conversion of aldehydes to 1,2-diketones in the liquid phase was enabled by using newly designed and developed ceria-zirconia-based high-entropy oxides (HEOs) as the actual catalysts. The synergistic effect of various cations incorporated in the same oxide structure (framework) was partially responsible for the efficiency of multicationic materials compared to the corresponding single-cation oxide forms. Furthermore, a clear, linear relationship between the Lewis acidity and the catalytic activity of the HEOs was observed. Due to the developed strategy, exclusively diketone-selective, recyclable, versatile heterogeneous catalytic transformation of aldehydes can be realized under mild reaction conditions.

Differential Precipitation of Mg(OH)2 from CaSO4·2H2O Using Citrate as Inhibitor-A Promising Concept for Reagent Recovery from MgSO4 Waste Streams.

In hydrometallurgical processing and acidic wastewater treatment, one of the neutralizing agents employed is MgO or Mg(OH)2. At the end of this process, the resulting solution, which is rich in SO42- and Mg2+ is treated with lime to remove (or minimize the amount) of these ions via the precipitation of Mg(OH)2 and CaSO4·2H2O (gypsum). In our work, an attempt was made to separate the two solids by increasing the induction time of the gypsum precipitation, thus regenerating relatively pure Mg(OH)2 which could be reused in wastewater treatments or hydrometallurgical processing circuits, and in this way, significantly enhancing the economic viability of the process. During our experiments, the reaction of an MgSO4 solution with milk of lime prepared from quicklime was studied. The effects of a range of organic additives, which can slow down the precipitation of gypsum have been assessed. The process was optimized for the most promising inhibiting agent-that is, the citrate ion. The reactions were continuously monitored in situ by conductometric measurements with parallel monitoring of solution pH and temperature. ICP-OES measurements were also carried out on samples taken from the reaction slurry. The composition of the precipitating solids at different reaction times was established by powder XRD and their morphology by SEM. Finally, experiments were carried out to locate the additive after the completion of the precipitation reaction to get information about its potential reuse.

Binding of Ca2+ Ions to Alkylbenzene Sulfonates: Micelle Formation, Second Critical Concentration and Precipitation.

Anionic surfactants, such as sodium linear alkylbenzene sulfonates (NaLAS), are utilized in various fields, including industry, household, and agriculture. The efficiency of their use in aqueous environments is significantly affected by the presence of cations, Ca2+ and Mg2+ in particular, as they can decrease the concentration of the surfactant due to precipitation. To understand cation-sulfonate interactions better, we study both NaLAS colloidal solutions in the presence of CaCl2 and precipitates forming at higher salt concentrations. Upon addition of CaCl2, we find the surface tension and critical micelle concentration of NaLAS to decrease significantly, in line with earlier findings for alkylbenzylsulfonates in the presence of divalent cations. Strikingly, an increase in the surface tension is discernible above 0.6 g L-1 NaLAS, accompanied by the decrease of apparent micelle sizes, which in turn gives rise to transparent systems. Thus, there appears to be a second critical concentration indicating another micellar equilibrium. Furthermore, the maximum salt tolerance of the surfactant is 0.1 g L-1 Ca2+, above which rapid precipitation occurs yielding sparingly soluble CaLAS2∙2H2O.

Biocompatible poly(ethylene succinate) polyester with molecular weight dependent drug release properties.

In the present study, we demonstrate that well-known molecular weight-dependent solubility properties of a polymer can also be used in the field of controlled drug delivery. To prove this, poly(ethylene succinate) (PES) polyesters with polycondensation time regulated molecular weights were synthesized via catalyst-free direct polymerization in an equimolar ratio of ethylene glycol and succinic acid monomers at 185 °C. DSC and contact angle measurements revealed that increasing the molecular weight (Mw, 4.3-5.05 kDa) through the polymerization time (40-80 min) increased the thermal stability (Tm= ∼61-80 °C) and slightly the hydrophobicity (Θw= ∼27-41°) of the obtained aliphatic polyester. Next, this biodegradable polymer was used for the encapsulation of Ca2+ channel blocker Nimodipine (NIMO) to overcome the poor water solubility and enhance the bioavailability of the drug. The drug/ polymer compatibility was proved by the means of solubility (δ) and Flory-Huggins interaction (miscibility) parameters (χ). The nanoprecipitation encapsulation of NIMO into PES with increasing Mw resulted in the formation of spherical 270 ± 103 nm NIMO-loaded PES nanoparticles (NPs). Furthermore, based on the XRD measurements, the encapsulated form of NIMO-loaded PES NPs showed lower drug crystallinity, which enhanced not only the water solubility but even the water stability of the NIMO in an aqueous medium. The in-vitro drug release experiments demonstrated that the release of NIMO drug could be accelerated or even prolonged by the molecular weights of PES as well. Due to the low crystallinity of PES polyester and low particle size of the encapsulated NIMO drug led to enhance solubility and releasing process of NIMO from PES with lower Mw (4.3 kDa and 4.5 kDa) compared to pure crystalline NIMO. However, further increasing the molecular weight (5.05 kDa) was already reduced the amount of drug release that provides the prolonged therapeutic effect and enhances the bioavailability of the NIMO drug.