Quantum-chemical investigation of interactions in supramolecular systems: cholesterol - bile acids - silica in aqueous solutions

Hypercholesterolemia significantly increases the risk of myocardial infarction associated with COVID-19. Along with pharmacological treatment, the possibility of the excretion of excess cholesterol from an organism by adsorption is also of great interest. The interaction of cholesterol with the surface of partially hydrophobized silica in aqueous solutions of bile acids was investigated by the PM7 method using the COSMO (COnductor-like Screening MOdel) solvation model. The distribution of electrostatic and hydrophobic potentials of molecules and complexes was calculated. The values of free Gibbs energy adsorption of bile acids on the surface of silica correlate with the distribution coefficients in the n-octanol-water system. The energy of interaction of cholesterol with bile acids affects its adsorption on silica. The stronger the bond of cholesterol with the molecules of bile acids, the less it is released from the primary micelles in solution and adsorbed on the surface.

Voltammetric study of cefotaxime at the macroscopic and miniaturized interface between two immiscible electrolyte solutions

The electrochemical behavior of cefotaxime (CTX+) was investigated at the polarized macro- and micro-interface between two immiscible electrolyte solutions (ITIES) by cyclic voltammetry and alternating current voltammetry. Miniaturization was achieved with fused silica microcapillary tubing entrapped in a polymeric casing. Scanning electron microscopy (SEM) was employed for the fabricated LLI support characterization. Voltammetric investigation of CTX+ at macro- and μ-ITIES allowed the determination of many physicochemical parameters, such as formal Galvani potential of the ion transfer reaction ($${\Delta }_{org}^{aq}{\varPhi}^{\prime }$$ Δ org aq Φ ′ ), diffusion coefficients (D), formal free Gibbs energy of the ion transfer reaction (∆G′aq → org), and water-1,2-dichloroethane partition coefficient ($${\log}{P}_{water/ DCE}^{CTX+}$$ log P w a t e r / D C E C T X + ). Additionally, based on the results obtained the analytical parameters including voltammetric sensitivity, limits of detection and the limits of quantification (in micromolar range) were calculated. The applicability of the developed procedures was verified in spiked still mineral and tap water samples. Graphical abstract

Kinetics, Thermodynamics and Equilibrium Studies for Gold Recovery from Diluted Waste Solution

2,2′-thiobisethanol dimethacrylate/ethylene glycol dimethacrylate copolymer (coP-TEDMA/EGDMA) was used as a sorbent for gold recovery from residual solutions resulting from the electroplating industry. Firstly, synthesized material was characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and confocal laser scanning microscopy. The sorption process mechanism was evidenced on the basis of kinetic, thermodynamic and equilibrium studies. To highlight this, the influence of solution pH, temperature and gold initial concentration on maximum sorption capacity was studied. The obtained experimental data were modeled using Langmuir, Freundlich and Sips sorption isotherms, and it was observed that the Sips one was better for describing the studied sorption process. Kinetic data were fitted using pseudo-first-order and pseudo-second-order kinetic models. Of these models, the studied process was better described by the pseudo-second-order model. The thermodynamic parameters free Gibbs energy (ΔG0), enthalpy (ΔH0), and entropy (ΔS0) were evaluated on the basis of the van’t Hoff equation. On the basis of the thermodynamic study, it was concluded that gold recovery on coP-TEDMA/EGDMA is a spontaneous and endothermic process.

Globular Aggregates Stemming from the Self-Assembly of an Amphiphilic N-Annulated Perylene Bisimide in Aqueous Media

Herein, we describe the synthesis of highly emissive amphiphilic N-annulated PBI 1 decorated with oligo ethylene glycol (OEG) side chains. These polar side chains allow the straightforward solubility of 1 in solvents of different polarity such as water, iPrOH, dioxane, or chloroform. Compound 1 self-assembles in aqueous media by π-stacking of the aromatic units and van der Waals interactions, favored by the hydrophobic effect. The hypo- and hypsochromic effect observed in the UV-Vis spectra of 1 in water in comparison to chloroform is diagnostic of H-type aggregation. Solvent denaturation experiments allow deriving the free Gibbs energy for the self-assembly process in aqueous media and the factor m that is indicative of the influence exerted by a good solvent in the stability of the final aggregates. The ability of compound 1 to self-assemble in water yields globular aggregates that have been visualized by TEM imaging.

Thermodynamics of phase transitions in the subsolidus domain of the FeO–MgO–TiO2 system

This paper gives consideration to the three-component FeO–MgO–TiO2 system that is a part of the four-component MgO–Al2O3–FeO–TiO2 system which serves to produce materials with valuable properties. The structure of binary FeO–TiO2 and MgO–TiO2 systems is described and the available data on the FeO–MgO–TiO2 system are analyzed. We present the thermodynamic data on all system compounds and calculate change of the free Gibbs energy in the temperature range of 800 to 1900 K for three exchange reactions. It was established that the triangulation of the FeO–MgO–TiO2 system changes in three following temperature ranges: at the temperatures of up to 1115 К, at 1115 to 1413 К (the restructuring of conodes here occurs) and above 1413 K (stable pseudobrookite is formed). It was shown that the following two-phase equilibria are stable: MgTi2O5–FeTiO3, FeTiO3–MgTiO3, MgTiO3–Fe2TiO4, Fe2TiO4–Mg2TiO4 and Mg2TiO4–FeO at the temperatures of up to 1115 K; MgTi2O5–FeTiO3, FeTiO3–MgTiO3, FeTiO3–Mg2TiO4, Fe2TiO4–Mg2TiO4 and Mg2TiO4–FeO in the temperature range of 1115 to 1413 K; and MgTi2O5–FeTi2O5, MgTi2O5–FeTiO3, FeTiO3–MgTiO3, FeTiO3–Mg2TiO4, Fe2TiO4–Mg2TiO4 and Mg2TiO4–FeO at the temperatures of above 1413 K.

Nb2O5-Ni3N heterojunction tuned by interface oxygen vacancy engineering for enhancement of electrocatalytic hydrogen evolution activity

The requirement of hydrogen adsorption free Gibbs energy (ΔGH*) approximating to 0 eV limits the hydrogen evolution reaction (HER) activity of most electrocatalysts in alkaline media. The construction of interface...

Recovery of Diamond and Cobalt Powders from Polycrystalline Drawing Die Blanks via Ultrasound Assisted Leaching Process—Part 2: Kinetics and Mechanisms

The leaching of industrial polycrystalline diamond (PCD) blanks in aqua regia at atmospheric pressure between 60 °C and 80 °C was performed using an ultrasound to improve the rate of cobalt removal in order to be able to reuse very expensive polycrystalline diamond. Because cobalt (20 wt.%) is used as a solvent catalyst in the production of PCD, its recovery is very important. The cleaned PCD are returned to the production process. Kinetic models were used in the study of cobalt dissolution from polycrystalline diamond blanks by measuring the declining ferromagnetic properties over time. For a better understanding of this leaching process, thermochemical aspects are included in this work. The lowest free Gibbs energy value was obtained with a low solid/liquid ratio and the full use of an ultrasound. A transition from a reaction-controlled to a diffusion-controlled shrinking core model was observed for PCD with a thickness greater than 2.8–3.4 mm. Intermittent ultrasound doubles the reaction rate constant, and the full use of ultrasound provides a 1.5-fold further increase. The obtained maximum activation energy between 60 °C and 80 °C is 20 kJ/mol, for a leaching of diamond blank with grain size of 5 µm.

Investigation of an adsorbent based on novel starch/chitosan nanocomposite in extraction of indigo carmine dye from aqueous solutions

Treatment of corn starch using pullulanase to prepare high yield of starch nanoparticles (StNPs) in a short time is one of the best ways of green industry of StNPs in comparison with other preparation procedures. Morphology of surface, particle size, function groups behavior and crystalline structure were investigated by using Scanning electron microscope (SEM), Dynamic light scattering (DLS), Transmission electron microscope (TEM), Fourier transforms infrared spectroscopy and X-ray diffraction. Starch nanoparticles can be used with chitosan to generate a novel composite to remove dyes from aqueous solutions. Indigo carmine dye was remediated with chitosan starch nanoparticle composite to evaluate the adsorption efficiency of such composite. Batch experiments were done to check the optimum pH, contact time, adsorbent dose, initial dye concentration and temperature to assess the kinetic data from isotherm of adsorption. The obtained results are fitted with pseudo second order and Langmuir isotherms. Free Gibbs energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of the sorption parameters indicated spontaneous and endothermic adsorption process.

Conformational Mobility Study in Mono Quinone Derivative of Calix[4]arene by Low Temperature NMR Spectroscopy

: Calix[4]monoquinone (3) has been synthesized by oxidation of rigid cone conformation of tripropoxy calix[4]arene (2), and conformational characteristics of this molecule have been studied by means of dynamic nuclear magnetic resonance (DNMR) and HH- correlated nuclear magnetic resonance spectroscopy (HH-COSY NMR). On the basis of the data that have been obtained, free Gibbs energy of activation (ΔG#) for quinone ring interconversion process of 3 was determined 12.3±0.05 Kcal/mol by coalescence approximation method.

Simulasi Docking Senyawa Aktif Daun Binahong Sebagai Inhibitor Enzyme Aldose Reductase

The metabolic syndrome is the cause of death around the world caused by diabetic mellitus. Binahong leaf is a kind of plant that is widely used to treat various diseases. This study aims to investigate the inhibitory activity of binahong leaves compound in inhibiting the aldose reductase which has role of converting glucose into sorbitol by docking simulation. The compound of binahong leaves consists of ursolic acid, vitexin, and oleonolic acid (ligand testing). These compound were taken from PubChem site, while aldose reductase enzyme (receptor) was obtained from the world protein bank with PDB 2HV5 code. This study incorporated in silica technique by using Auto dock vina software, Discovery Studio and Ligplot as visualization. The result of grid box optimization by redocking comparative ligand was 0.7Å RMSD. The docking result showed that the free Gibbs energy (∆G) of aldose reductase was (-11.7), Vitexin (-8.3), Ursolic acid (-7.7) and Oleonolic acid (-8.6). These value suggested that there was a stable inhibition reaction from the binahong leaves compound and the comparative ligand. Based on the Lipinski Rule, the composition of binahong leaves compound meets the Lipinski Rule criteria which means this medicine can be used orally except for vitexin and comparative ligands of zopolrestate which exceed the number of the atom.