FORMATION OF HUMBOLDTINE DURING THE DISSOLUTION OF HEMATITE IN OXALIC ACID – DENSITY FUNCTIONAL THEORY (DFT) CALCULATIONS AND EXPERIMENTAL VERIFICATION

Understanding the reactions taking place in the hematite-oxalic acid system is important in order to clean iron oxides from filters and to remove iron from mineral concentrates. Previous studies reported the formation of an unwanted solid phase during this process. The objective of the current work, therefore, was to visualize and rationalize the iron dissolution steps taking place in the hematite–oxalic acid reaction by combining density functional theory (DFT) calculations and experimental data. The results of DFT calculations indicated that a precipitate was formed in this reaction; XRD analysis of the solid phase after the dissolution experiment revealed the formation of humboldtine as the precipitate. The attachment of oxalate on the hematite surface and the reduction of Fe(III) to Fe(II) were key steps for humboldtine formation. Both simulations and the experimental results showed that greater oxalic acid concentrations yielded more precipitate, suggesting a simple and novel route to synthesize humboldtine, a material which is relevant to the demand for clean energy.

Freeze-Drying Ethylcellulose Microparticles Loaded with Etoposide for In Vitro Fast Dissolution and In Vitro Cytotoxicity against Cancer Cell Types, MCF-7 and Caco-2

The aim of this study was to improve the solubility of etoposide–ethylcellulose (ET–ETO) microparticles using the freeze-drying technique. Ethylcellulose (EC) microparticles loaded with etoposide (ETO) were prepared with different drug–polymer molar ratios of 1:1, 1:3, 1:6, and 1:20 by the solvent evaporation method. The size of the prepared microparticles was 0.088 µm. The results showed that the amount of ETO encapsulated into the microparticles was 387.3, 365.0, 350.0, and 250 µg/50 mg microparticles for microparticles with drug–polymer ratios of 1:1, 1:3, 1:6, and 1:20, respectively. The FT-IR spectra showed no chemical interaction between ETO and the polymer in the solid state. The results obtained from the dissolution experiment showed that the freeze-dried microparticles were stable in 0.1 N HCl (gastric pH) for 2 h. At pH 7.4, the ETO release was 60 to 70% within the first 15 min and approximately 100% within 30 min. Results from the application of different dissolution models showed that the equations that best fit the dissolution data for the ET–ETO microparticles at pH 7.4 were the Higuchi and Peppas model equations. The in vitro cytotoxicity assay of free ETO and freeze-dried microspheres prepared in this study with a drug–polymer ratio of 1:1 was performed in two mammalian cancer cell lines, MCF-7 (for bone cancer of the mammary organ) and Caco-2 (for mammalian epithelial colorectal adenocarcinoma). The results showed that the half-maximal inhibitory concentrations (IC50 values) for ETO and freeze-dried ET–ETO microparticles were 18.6 µM and 27.1 µM, respectively. In conclusion, freeze-dried ET–ETO is a promising formulation for developing a fast-dissolving form of ETO with a significant antiproliferative activity against the tested cell lines used in this study. It is a promising formulation for local duodenal area targeting.

Dissolution, Solubility, and Stability of the Basic Ferric Sulfate-Arsenates [Fe(SO4)x(AsO4)y(OH)z·nH2O] at 25–45°C and pH 2–10

Basic ferric sulfate-arsenates [FeSAsOH, Fe(SO4)x(AsO4)y(OH)z·nH2O] were prepared and characterized to study their potential fixation of arsenic in the oxidizing and acidic environment through a dissolution for 330d. The synthetic solids were well-shaped monoclinic prismatic crystals. For the dissolution of the sample FeSAsOH–1 [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O] at 25–45°C and initial pH 2, all constituents preferred to be dissolved in the order of AsO43− > SO42− > Fe3+ in 1–3 h, in the order of SO42− > AsO43− > Fe3+ from 1–3 h to 12–24 h, and finally in the order of SO42− > Fe3+ > AsO43−. The released iron, sulfate, and arsenate existed dominantly as Fe3+/Fe(OH)2+/FeSO4+, HSO4−/SO42−/FeSO4+, and H3AsO40/H2AsO4−, respectively. The higher initial pHs (6 and 10) could obviously inhibit the release of Fe3+ from solid into solution, and the solid components were released in the order of SO42− > AsO43− > Fe3+. The crystal tops were first dissolved, and the crystal surfaces were gradually smoothed/rounded until all edges and corners disappeared. The dissociations were restricted by the Fe-O(H) breakdown in the FeO6 octahedra and obstructed by the OH− and AsO4 tetrahedra outliers; the lowest concentration of the dissolved arsenic was 0.045 mg/L. Based on the dissolution experiment at 25°C and pH 2, the solubility products (Ksp) for the basic ferric sulfate-arsenate [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O], which are equal to the ion activity products (logˍIAP) at equilibrium, were calculated to be -23.04 ± 0.01 with the resulting Gibbs free energies of formation (ΔGfo) of −914.06 ± 0.03 kJ/mol.

New Cocrystals of Antipsychotic Drug Aripiprazole: Decreasing the Dissolution through Cocrystallization

Cocrystallization is an important route to tuning the solubility in drugs development, including improving and reducing. Five cocrystals of aripiprazole (ARI) with resveratrol (RSV) and kaempferol (KAE), ARI-RSV, ARI2-RSV1·MeOH, ARI-KAE, ARI-KAE·EtOH, ARI-KAE·IPA, were synthesized and characterized. The single crystal of ARI2-RSV1·MeOH, ARI-KAE·EtOH, and ARI-KAE·IPA were analyzed by single crystal X-ray diffraction (SCXRD). The SCXRD showed multiple intermolecular interactions between API and the coformers, including hydrogen bond, halogen bond, and π-π interactions. Dissolution rate of the two nonsolvate ARI-RSV and ARI-KAE cocrystals were investigated through powder dissolution experiment in pH = 4.0 acetate buffer and pH = 6.8 phosphate buffer. The result showed that RSV could reduce the dissolution rate and solubility of ARI in both medium through cocrystallization. However, KAE improved the dissolution rate and solubility of ARI in pH = 4.0 medium, on the contrary, the two solubility indicators of ARI were both reduced for ARI-KAE cocrystal.

Wormhole dynamics, competition for the flow and changes in transport behavior: an intermediate-scale experiment

<p>Salt flats (Salares) are complex evaporitic systems of economic interest and environmental value. On the one hand, these aquifers are usually exploited for variety of minerals, including dissolved species (e.g. Lithium and Potassium) extracted from the brines. On the other hand, the genesys of salares favors that they are surrounded by uncommon ecosystems, which must be protected. In this context, it is fear that brine pumping might favor the development of dissolution channels (Wormholes) that could connect the Salar nucleus with the environmental sensitive surroundings. Thus, a full understanding of the conditions and processes involved in wormhole formation and evolution has to be achieved. The hydraulic and geochemical conditions for conduits growth have been widely discussed in carbonate environments, while little has been done in halitic and gypsum environments. But we unknowledge experimental works aimed at understanding wormhole dynamics and the mechanism of competition for the flow that influence dissolution pattern evolution.</p><p>In this study, we want to improve the understanding of multiple wormholes growth in the context of wormhole competition and consequent changes in transport behaviors. For that purpose, we designed and performed a laboratory intermediate-scale tank experiment under controlled conditions. Halite in the form of granular medium is used to reproduce the aquifer. Hydrodynamics and geochemical conditions are set as to reproduce a dominant wormhole dissolution regime. Several coloured tracer tests are carried out to characterize the medium before, during and after the dissolution experiment.  Tracer concentration, hydrogeochemical and flow parameters, as well as tank images are continuously recorded. In particular, the use of fluorescent tracer jointly with image processing analysis highlights wormholes growth, shape and propagation through the medium at different times. Experimental results allow visualizing and analyzing several features related to wormhole competition, e.g. wormhole growth rate and density evolution, as well the redistribution of the flow towards areas where dominant wormholes are developing. Results are compared to available numerical and analytical solutions. Lastly, the interpretation of BTCs allows to understand changes in flow and trasport behavior and related processes, given the developing dissolution pattern.</p>

Subpixel determination of wormhole tip position in 4D tomography of dissolving limestone cores

<p>Dissolution of porous rocks by reactive fluids is a highly nonlinear process resulting in a variety of dissolution patterns, the character of which depends on physical conditions such as flow rate and reactivity of the fluid. Long, finger-like dissolution channels, “wormholes”, are the main subject of interest in the literature, however, the underlying dynamics of their growth remains unclear. </p><p>While analyzing the tomography data on wormhole growth.  one open question is to define the exact position of the tip of the wormhole. Near the tip the wormhole gradually thins out and the proper resolution of its features is hindered by the finite spatial resolution of the tomographs. In particular, we often observe in the near-tip region several disconnected regions of porosity growth, which - as we hypothesized - are connected by the dissolution channels at subpixel scale. In this study, we show how these features can be better resolved by using numerically calculated flow fields in the reconstructed pore-space. </p><p>We used 70 micrometers, 16-bit grayscale X-ray computed microtomography (XCMT) time series scans of limestone cores, 14mm in diameter and 25mm in length. Scans were performed during the entire dissolution experiment with an interval of 8 minutes. These scans were further processed using a 3-phase segmentation proposed by Luquot et al.[1], in which grayscale voxels are converted to macro-porosity, micro-porosity and grain phases from their grayscale values. The macro-porous phase is assigned a porosity of 1, while the grain phase is assigned 0. Micro-porous regions are assigned an intermediate value determined by linear interpolation between pore and grain threshold using grayscale values. An OpenFOAM based, Darcy-Brinkman solver, porousFoam, is then used to calculate the flow field in this extracted porosity field. </p><p>Porosity contours reconstructed from the tomographs show some disconnected porosity growth near the tip region which later become part of the wormhole in subsequent scans. We have used a novel approach by including the micro-porosity phase in pore-space to calculate the flow-fields in the near-tip region. The calculated flow fields clearly show an extended region of focused flow in front of the wormhole tip, which is a manifestation of the presence of a wormhole at the subpixel scale. These results show that micro-porosity plays an important role in dissolution and 3-phase segmentation combined with the flow field calculations is able to capture the sub-resolved dissolution channels. </p><p> </p><p> [1] Luquot, L., Rodriguez, O., and Gouze, P.: Experimental characterization of porosity structure and transport property changes in limestone undergoing different dissolution regimes, Transport Porous Med., 101, 507–532, 2014</p>

Experimental Investigation of Permeability Evolution on Sandstone in Triaxial and Long-Term Dissolution Experiment

The temporal permeability and damage evolutions of low-permeability sandstone cores during triaxial and long-term dissolution experiments were measured using a triaxial-flow system. Three triaxial experiments were performed on sandstone cores having initial permeability ranging from 78 × 10 − 18 m 2 to 120 × 10 − 18 m 2 . Two sets of long-term dissolution experiments were conducted on cracked sandstone cores. All dissolution experiments were performed at room temperature and using a 10 g/L H2SO4 and 0.2 g/L H2O2 input solution. Permeability evolution was determined using Darcy’s law. The cores experienced an average increase of 25% in permeability in the dissolution experiment and 900%~1500% increase at the end of the experiment. The dissolution was fairly homogeneous during the long-term experiments whether on the 1 mm scale or the 10 μm scale. The relationship between damage and permeability was speculated and its correlation coefficient has been proved to be close to 1. These results suggest that hydraulic fracturing works well in permeability increase in low-permeability sandstone reservoir.

Lyophilization-free proliposomes for sustained release oral delivery of hydrophobic drug (cinnarazine): a comparative study

Objectives Cinnarizine is used for the treatment of vestibular disorders. However, its poor solubility limits its clinical uses due to many challenges. Liposomes were utilised to improve the release profile of many poorly soluble drugs. However, liposomes face many stability challenges during the storage period. This study aims to develop proliposomes designed for the oral delivery of cinnarizine with enhanced stability characteristics. Methods Three cinnarizine entrapping Proliposomal formulations were prepared with different ingredients and compared with their liposomal counterparts. Both vesicular approaches were characterised for their particle size, encapsulation efficiency, drug release and stability. Results The proliposomes were superior to liposomes in their stability and release profiles. Although no significant changes were noticed between the encapsulation efficiency percentage of the liposomal and proliposomal formulations on the day of preparation, storing the formulations for two weeks ended up with significant leakage of the drug from liposomes (p < 0.05) due to stability issues, but not in proliposomes. Moreover, the proliposomes released 100% of cinnarizine throughout the dissolution experiment in gastric fluid in comparison with the total released drug of 70% from the liposomes. Conclusions Proliposomes provided a successful approach to deliver lipophilic drugs orally to improve their pharmacokinetic properties by converting their crystalline nature into more amorphous agents.

Quasi-Equilibrium and Unsteady Mass Transfer of Low-Grade Bloedite in the Process of Static Water Dissolution

Hydrometallurgical extraction and treatment of bloedite waste is one necessity for the sustainable development of sodium sulfate subtype salt lake mining areas, but the industrial dissolution of bloedite is not stable. One of the reasons for this is the unsteady mass transfer of dissolved electrolytes in water according to the diffusion model and static water dissolution experiment in this work. The diffusion behaviors of aqueous Na2SO4 and MgSO4 released from bloedite in water are similar, and their mass transfer coefficients decrease in a nonlinear manner as the diffusion process continues. Within 720 h of dissolution time, there is a quasi-steady-state quasi-linear stage of rapid increase in the solute concentration of leaching water, and a water depth of 20–40 mm is recommended as the optimal dissolution depth. Under such operating conditions, the amount of evaporated water required for salt production decreases in a quasi-linear manner with respect to dissolution time. However, after 720 h of dissolution and extraction time, the growth rate of brine concentration slows. The information provided by the model can be used in practice as a quantitative reference for bloedite recycling.