Separation of Rare-Earth Elements from Nitrate Solutions by Solvent Extraction Using Mixtures of Methyltri-n-octylammonium Nitrate and Tri-n-butyl Phosphate

The article presents data on the solvent extraction separation of rare-earth elements (REEs), such as La(III), Ce(III), Pr(III), and Nd(III), using synergic mixtures of methyltrioctylammonium nitrate (TOMANO3) with tri-n-butyl phosphate (TBP) from weakly acidic nitrate solutions. Specifically, experimental results on separation of REEs, for the pair Ce(III)/Pr(III) for quaternary mixtures of REEs (La(III), Ce(III), Pr(III), Nd(III)) and for the pair La(III)/Pr(III) for solutions containing La(III), Pr(III), and Nd(III), are presented. It was shown that effective separation for the pair Ce(III)/Pr(III) from a solution containing 219 g Ce(III)/L, 106 g La(III)/L, 20 g Pr(III)/L, 55 g Nd(III)/L, and 0.1 mol/L HNO3, was achieved using 56 steps of a multistage, counter-current solvent extraction cascade with scrubbing, at an organic-to-aqueous phase volume ratio (O/A) equal to 2/1 on the extraction section and O/A equal to 4/1 on the scrubbing section, using 3.3 mol/L solutions of the mixture TOMANO3-TBP with molar ratio 0.15:0.85 in dodecane. Separation for the pair La(III)/Pr(III) could be achieved using a solvent extraction cascade with scrubbing in 32 steps at O/A equal to 2/1 on the extraction section and O/A equal to 2.8/1 on the scrubbing section of the solvent extraction cascade from a solution containing 258 g La(III)/L, 58 g Pr(III)/L, 141 g Nd(III)/L, and 0.1 mol/L HNO3 with 3.0 mol/L solution of the mixture TOMANO3-TBP with molar ratio 0.2:0.8 in dodecane.

Synthesis Factors Dependence of Magnetic Properties of CoFe2O4 and CoFe2-xGdxO4 Semicrystalline Nanoparticles with desired Morphology through Hydrothermal Procedure

In the present study, CoFe2O4 and CoFe2-xGdxO4 nanoparticles were synthesized by the hydrothermal process. The CoFe2O4 nanoparticles were synthesized at different temperatures (70oC, 100oC, 150oC, and 200oC), molar ratio of CoCl2/ FeCl3 (0/2, 0.75/2, 1/2, 1.5/2, and 2/2). Gadolinium-doped cobalt ferrite (CoFe2-xGdxO4) nanoparticles have also been synthesized with Gd/Fe molar ratios of 0.18 and 0.53. The XRD patterns indicate that cobalt ferrite and Gadolinium-doped cobalt ferrite nanoparticles have been successfully synthesized without impurities with a medium degree of crystallinity. The XRD patterns show that by increasing the synthesis temperature from 70oC to 200oC, the size of the nanoparticles decreased from 50.49nm to 32.45nm while the morphology of the nanoparticles also changed from a shapeless and agglomerated state to a spherical shape. The XPS curve illustrated several peaks corresponding to Fe+3, Co+2, and O 1s. The binding energies for Co and Fe were consistent with Fe 2p and Co 2p binding energies for cobalt ferrite nanoparticles. The magnetic saturation value (Ms) increased from 17.253 emu/g to 54.438 emu/g with a rise in the synthesis temperature. The effects of FeCl3/CoCl2 molar ratio on the magnetic properties showed the highest value of Ms (54.438 emu/g) and the coercivity (HC) of 744.56 Oe for a 2/1 molar ratio. The addition of gadolinium to the composition resulted in a reducing of the magnetic properties of nanoparticles; accordingly, the amount of saturated magnetization was reduced to 22.469 emu/g. Another effect of gadolinium dopant in the composition was a change in nanoparticle morphology from spherical to rod shape. The final aim of this study was to investigate the possible utilization of CoFe2O4 and CoFe2-xGdxO4 nanoparticles in medical treatment in the near future.

A Development Strategy of Tailor-made Natural Deep Eutectic Solvents for the Enhanced Extraction of Hydroxynaphthoquinones from Alkanna tinctoria Roots

Natural hydroxynaphthoquinone enantiomers (HNQs) are well-described pharmaceutical and cosmeceutical agents especially present in the roots of Alkanna tinctoria (L.) Tausch, a species native to the Mediterranean region. In this work, eco-friendly natural deep eutectic solvents (NaDESs) were developed for the selective extraction of these compounds. An extensive screening was performed using more than sixty tailor-made NaDESs. The impact of the intrinsic physicochemical properties on the HNQs extraction efficiency as well as the specificity towards the different enantiomeric pairs was thoroughly investigated. As a result of a multivariate analysis and of the one factor-a-time solvent optimization, the eutectic mixture composed of levulinic acid and glucose (LeG) using a molar ratio of 5:1 (molHBA:molHBD) and 20% of water (w/w) was found as the most appropriate mixture for the highest extraction efficiency of HNQs. Further optimization of the extraction process was attained by response surface methodology, using a temperature of 45 °C, a solid-to-liquid ratio of 30 mg/mL, and an extraction time of 50 min. A maximum extraction output of 41.72 ± 1.04 mg/g was reached for HNQs, comparable to that of the commonly used organic solvents. A solid-phase extraction step was also proposed for the recovery of HNQs and for NaDESs recycling. Our results revealed NaDESs as a highly customizable class of green solvents with remarkable capabilities for the extraction of HNQs.

Effect of Aluminum Incorporation on the Reaction Process and Reaction Products of Hydrated Magnesium Silicate

In this study, we investigated the impact of aluminium ion (Al3+) incorporation on the microstructure and the phase transformation of the magnesium silicate hydrate system. The magnesium silicate hydrate system with aluminium was prepared by mixing magnesium oxide and silica fume with different aluminium ion contents (the Al/Si molar ratios of 0.01, 0.02, 0.05, 0.1, 0.2) at room temperature. The high degree of polymerization of the magnesium silicate hydrate phases resulted in the limited incorporation of aluminium in the structure of magnesium silicate hydrate. The silicon-oxygen tetrahedra sites of magnesium silicate hydrate layers, however, were unable to substitute for silicon sites through inverted silicon-oxygen linkages. The increase in aluminium ion content raised the degree of polymerization of the magnesium silicate hydrate phases from 0.84 to 0.92. A solid solution was formed from residual aluminum-amorphous phases such as hydroxyl-aluminum and magnesium silicate hydrate phases. X-ray diffraction (XRD), field emission scanning electron microscope (F-SEM), and 29Si and 27Al MAS NMR data showed that the addition of Al3+ promotes the hydration process of MgO and has an obvious effect on the appearance of M-S-H gel. The gel with low aluminum content is fluffy, while the gel with high aluminum content has irregular flakes. The amount of Al3+ that enters the M-S-H gel increased with the increase of Al3+ content, but there was a threshold: the highest Al/Si molar ratio of M-S-H gel can be maintained at about 0.006.

One-pot synthesis of the new Hydroxamic acid and its complexes with metals

A one-pot conversion of 2-hydroxy-1-naphthoic aldehyde to hydroxamic acid was described. An efficient photoorganocatalytic method of synthesis was developed. The obtained hydroxamic acid was identified by various physicochemical methods such as IR, UV- and NMR-spectroscopy. Solid colored complexes of copper (II) and iron (II), respectively, green and brown colours with the obtained hydroxamic acid were synthesized in ethanol medium for the first time. The molar ratio of ligand and metal in the complex was 2:1. Their structures were established using IR, UV- spectroscopy and thermogravimetric analysis.

MgAl2O4 spinel-type as highly efficient catalyst for one-pot synthesis of 4H-pyrans

Background: Pyran is an heterocyclic oxygen-containing compound that displays a wide range of therapeutic activities. Additionally, pyran is also one of the important structural subunits widely found in pharmaceuticals products. This makes it a recent focus for researchers from the industry and academic institutions. Herein, we reported an efficient and environmentally friendly one-pot strategy for the synthesis of bioactive 4H-pyran compounds via a multicomponent reaction of ethyl acetoacetate, malononitrile and substituted aromatic aldehydes in the presence of the heterogeneous spinel catalyst ( MgAl2O4 ) under mild conditions (room temperature and green solvents). The MgAl2O4 nanocatalyst was prepared from Mg/Al-LDH with a molar ratio 3 of Mg2+/Al3+ by heat treatment at 800°C. The samples were studied by a various characterization techniques such as XRD, TG-dTG, FT-IR and N2 adsorption-desorption. Good to excellent yields and facile separation of the catalyst from the reaction mixture are two of the most appealing features of this approach. Thus, bioactive molecules with pyran units may have fascinating biological properties. An efficient and green strategy for the one-pot synthesis of bioactive 4H-pyran compounds has been described. The pyrans heterocycles were produced by multicomponent reaction of ethyl acetoacetate, malononirile and substituted aromatic aldehydes in the presence of MgAl2O4 spinel nanocatalyst under mild conditions (room temperature and green solvents). MgAl2O4 nanocatalytst was prepared from Mg/Al-LDH with a molar ratio 3 of Mg2+/Al3+ by thermal treatment at 800°C. The samples were investigated by various characterization techniques such as XRD, TG-dTG, FT-IR and N2 adsorption-desorption. The following are the appealing qualities of this unique strategy including good to exceptional yields, and ease of separation of catalyst from the reaction mixture. Thus, the obtained bioactive compounds containing pyrans motif can be exhibiting interested biological activities. Methods: The substituted 4H-pyran compounds were carried out by condensation reaction of substituted aromatic aldehydes, ethyl ethyl acetoacetate and malononirile by using MgAl2O4 nanocatalyst under sustainable conditions. Objective: To develop an efficient methodology for synthesis of 4H-pyran heterocyclic molecules may have interesting applications in biology using a heterogeneous and easily synthesized catalyst. Results: This procedure outlines the synthesis of bioactive compounds in good yields and with ease of catalyst extraction from the reaction mixture under sustainable reaction conditions. Conclusion: In conclusion, it is important to reiterate that a spinel nanostucture has been successfully prepared and fully characterized using different physicochemical analysis methods. The catalytic activity of this heterogeneous catalyst was examined through the one-pot condensation of aryl benzaldehyde, malononitrile and ethyl acetoacetate. Therefore, we have developed a green method for the preparation of 4H-pyrans derivatives using MgAl2O4 as an efficient heterogeneous catalyst. The reactions were performed under green conditions, which have many benefits such as undergoing a simple procedure, good to excellent yields and easy to separate the catalyst.

Thermodynamic modelling of roasting of molybdenum sulphide concentrate with calcium hydroxide

This work aims to determine the conditions for the CaMoO4, CaSO4, Ca(ReO4)2 formation during oxidation of MoS2 and ReS2 in the presence of Ca(ОН)2. The concentrate from the Yuzhno-Shameyskoye deposit in the Sverdlovsk region, having 37% wt. Мо and 0.005% wt. Re, was selected as a feedstock for thermodynamic modelling of sweet roasting in the presence of Ca(OH)2. To determine the optimal amount of calcium-containing additives, the thermodynamic modelling was carried out using the following mass ratios: molybdenum concentrate: Ca(OH)2 = 1:0.8, 1:1, 1:1.2 and 1:1.5 in the temperature range of 100–800°С, with a step of 100°С, system pressure of 0.1 MPa in the air (molar ratio: molybdenum concentrate + Ca(OH)2: air = 1:5). The content of all sample components in moles was entered into the HSC 6.1 software package. The main reactions associated with the sweet roasting of molybdenum concentrate in the presence of calcium hydroxide were shown. It was established that the main phases formed as a result of roasting comprise CaSO4, CaSO3, MoO3, CaMoO4, CaMoO3 and CaReO4. The effect of temperature on the formation of the main gaseous products was studied under different mass ratios of molybdenum concentrate and Ca(OH)2. It was found that up to 600°C, with molybdenum concentrate to Ca(OH)2 ratio of 1:1, the concentrations of released sulphurous anhydride are lower than the maximum permissible concentrations. The calculated thermodynamic data was used for modelling the roasting process of molybdenum concentrate with calcium hydroxide. An optimal ratio necessary for the successful process operation was established: molybdenum concentrate: Ca(OH)2 = 1:1 by weight. Thermodynamic modelling showed that, in the temperature range of 100–600°С when using Ca(OH)2, no rhenium and molybdenum loss is observed, the release of sulfur is less than 10 mg/m3.

Insulin Complexation with Cyclodextrins—A Molecular Modeling Approach

Around 5% of the population of the world is affected with the disease called diabetes mellitus. The main medication of the diabetes is the insulin; the active form is the insulin monomer, which is an instable molecule, because the long storage time, or the high temperature, can cause the monomer insulin to adapt an alternative fold, rich in β-sheets, which is pharmaceutically inactive. The aim of this study is to form different insulin complexes with all the cyclodextrin used for pharmaceutical excipients (native cyclodextrin, methyl, hydroxyethyl, hydroxypropyl and sulfobutylether substituted β-cyclodextrin), in silico condition, with the AutoDock molecular modeling program, to determine the best type of cyclodextrin or cyclodextrin derivate to form a complex with an insulin monomer, to predict the molar ratio, the conformation of the complex, and the intermolecular hydrogen bonds formed between the cyclodextrin and the insulin. From the results calculated by the AutoDock program it can be predicted that insulin can make a stable complex with 5–7 molecules of hydroxypropyl-β-cyclodextrin or sulfobutylether-β-cyclodextrin, and by forming a complex potentially can prevent or delay the amyloid fibrillation of the insulin and increase the stability of the molecule.

Synthesis and Characterization of Phosphoric Silica Catalyst from Bamboo Leaves for Production of Triacetin

In this research, the bamboo leaf shows promise as an alternative raw material for silica production. This study investigated the performance of heterogeneous catalyst prepared from silica derived bamboo leaf ash after that impregnated with phosphoric acid at ratio various. The catalyst was characterized by X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscope Energy Dispersive X-Ray Spectroscopy (SEM-EDS), Brunauer Emmet Teller (BET) and Barrett, Joyner and Halenda (BJH) method and triacetin product analyzed by GC-MS. The optimum condition phosphoric silica catalyst was obtained at phosphoric silica molar ratio of 1:2 and employed in the acetylation of glycerol, respectively. As result, 24 % selectivity for triacetin was obtained in the presence of catalytic amount 5%, molar ratio 1:9 at 100 °C for 4 hours. Bamboo leaf derived phosphoric silica calcined showed high potential to be used as an easy to prepare and high-performance solid catalyst for industrial scale.