Reaction in Dry Media: Silica Gel Supported Ferric Chloride Catalyzed Synthesis of 1,8-Dioxo-octahydroxanthene Derivatives

Herein, we describe a green procedure for the one-pot preparation of 1,8-dioxo-octahydroxanthene derivatives by condensation of dimedone and substituted benzaldehydes in the presence of FeCl ₃ -SiO ₂ as an efficient and heterogeneous catalyst under microwave irradiation and thermal conditions. This method has the advantages of high yields, cleaner reactions, efficient and cost-effective method, simple methodology, short reaction times, easy workup, and greener conditions.     

Cathodic electrodeposition and characterization of nanostructured Y2O3 from chloride solution Part I: Effect of current density

Nanoparticles, nanospheres and nanorods of Y(OH)₃ and Y₂O₃ were prepared via cathodic electrodeposition from chloride bath through applying different current densities. First, yttrium hydroxide precursors were cathodically grown on the cathode surface at the current densities of 2, 1, 0.5, 0.25 and 0.1 mA cm^?2. Then hydroxide powders were heat-treated at 600°C for 3 h. The composition, crystal structure and morphology of the prepared oxide and hydroxide products were investigated by means of differential scanning calorimetery (DSC), X-ray diffraction (XRD), scanning and transmission electron microscopes (SEM and TEM) and FT-IR spectroscopy. Mechanism of base electrogeneration at the applied conditions, and intercalation of chloride ions in the deposit structure during the electrodeposition were proposed and confirmed by the XRD and TG analyses. The results showed that the structural and morphological properties of the products are directly dictated by the applied current density and it can be recognized as the main factor affecting on the cathodic electrodeposition of Y₂O₃.     

“On-water” organic synthesis: <Emphasis Type="SmallCaps">l</Emphasis>-proline catalyzed synthesis of pyrimidine-2,4-dione-, benzo[<Emphasis Type="Italic">g</Emphasis>]- and dihydropyrano[2,3-<Emphasis Type="Italic">g</Emphasis>]chromene derivatives in aqueous media

In this work, functionalized pyrimidine-2,4-dione-, benzo[g]-, and dihydropyrano[2,3-g]chromene derivatives have been synthesized via a Michael addition of 2-hydroxy-1,4-naphthoquinone or 2,5-dihydroxy-1,4-benzoquinone to the Knoevenagel condensation product of an aldehyde with Meldrum’s acid, dimedone or barbituric acid in the presence of a catalytic amount of l-proline under refluxing conditions in water in good to excellent yields.     

Synthesis, crystal structures and electrochemical properties of CoIII complexes with hexadentate ligand containing thioether-amidopyridyl donor set

Two new cobalt(III) complexes of the hexadentate ligand [1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane] (H₂bpctb) with N₄S₂ donor set atoms have been synthesized. A reaction of Co(CH₃COO)₂·4H₂O with (H₂bpctb) leads to the formation of [Co^III(bpctb)]PF₆ (1) having a CoN₂(pyridine)N′₂(amide)S₂(thioether) coordination by symmetric bpctb^2? ligand. A similar reaction under slightly different conditions, however, gives [Co^III(L ^a )(L ^b )] (2), resulting from a C–S bond cleavage reaction triggered by an acetate ion as a base, having CoN₂(pyridine)N′₂(amide)S(thioether)S′(thiolate) coordination. These two Co(III) complexes have been characterized by elemental analyses and spectroscopic methods, and the crystal and molecular structures of [Co^III(bpctb)]PF₆ (1) in the form of the solvate (1·MeOH·H₂O) and of [Co^III(L ^a )(L ^b )] (2) have been determined by X-ray crystallography. The Co atoms of both complexes exhibit distorted octahedral geometry. The electrochemical investigation of [Co(bpctb)]PF₆·MeOH·H₂O (1·MeOH·H₂O) and [Co^III(L ^a )(L ^b )] (2) by cyclic voltammetry reveals a reversible Co^III–Co^II redox process at E _1/2 = ?0.32 V (ΔE _p = 80 mV); for 1, and E _1/2 = ?0. 87 V (ΔE _p = 70 mV) for 2.     

Unfolding mechanism of PHD2 as a vital protein: all-atom simulation approach

Prolyl hydroxylase domain 2 containing protein (PHD2) is a central protein in regulation of cellular response to hypoxia. This protein controls the responses of cell to oxygen level via the regulation of hypoxia inducible factor (HIF) stability. HIF induces the expression of many genes, especially ones orchestrate angiogenesis. There are some reports that mentioned in some tumor types the level of HIF is high in spite of the presence of wild-type PHD2 and normoxic environment. Therefore, the possibility of PHD2 misfolding in some cancer cells arises. Studying such important protein unfolding pathway is insightful for possible therapeutic approaches. In this study, the unfolding pathway of PHD2 illustrates utilizing molecular dynamics simulation of protein thermal denaturation. Based on current study results, we represent the possible mechanisms of PHD2 unfolding in detail. The possible intermediates of PHD2 thermal unfolding are characterized, and the most venomous state of its unfolding pathway is introduced.     

A selective electromembrane extraction of uranium (VI) prior to its fluorometric determination in water

A novel method for the selective electromembrane extraction (EME) of U⁶⁺ prior to fluorometric determination has been proposed. The effect of extraction conditions including supported liquid membrane (SLM) composition, extraction time and extraction voltage were investigated. An SLM composition of 1% di-2-ethyl hexyl phosphonic acid in nitrophenyl octyl ether (NPOE) showed good selectivity, recovery and enrichment factor. The best performance was achieved at an extraction potential of 80 volts and an extraction time of 14 minutes Under the optimized conditions, a linear range from 1 to 1000 ng mL⁻¹ and LOD of 0.1 ng mL⁻¹ were obtained for the determination of U⁶⁺. The EME method showed good performance in sample cleanup and the reduction of the interfering effects of Mn²⁺, Zn²⁺, Cd²⁺, Ni²⁺, Fe³⁺, Co²⁺, Cu²⁺, Cl⁻ and PO₄³⁻ ions during fluorometric determination of uranium in real water samples. The recoveries above 54% and enrichment factors above 64.7 were obtained by the proposed method for real sample analysis.     

Ultra‐Trace Silver Determination in Biological and Water Samples by Electrothermal Atomic Absorption Spectrometry after Electrodeposition on a Graphite Probe

A rapid and simple procedure was developed for selective and sensitive determination of ultra‐trace silver in biological and environmental samples using the electrodeposition on a graphite probe modified with palladium followed by electrothermal atomic absorption spectrometry. Several experimental parameters for the electrodeposition, such as deposition potential, electrolyte concentration, pH of solution and deposition time were optimized. The calibration graph after preconcentration was linear in the range of 10‐250 ngL^?1 with correlation coefficient of 0.9989 under the optimum conditions for procedure. The limits of detection (LOD) and quantification (LOQ) base on (3σ) and (10σ) were 2.8 ngL^?1 and 9.4 ngL^?1 respectively. Related standard deviation (RSD) for eight replicate measurements of 100 ngL^?1 silver was 4.3%. Samples were digested completely in a closed microwave digestion system using only perchloric acid, and interference owing to various cations was also investigated. The proposed procedure was successfully applied to determine silver in blood, urine and some environmental samples with satisfactory analytical results.     

High‐Efficiency Conversion of Trimethylsilyl Ethers to Their Corresponding Ethers using Carbon‐Based Solid Acid as a New Catalyst in Heterogeneous Mixtures

Carbon‐based solid acid was used as a new catalyst for conversion of trimethylsilyl ethers to their corresponding ethers in heterogeneous mixtures. The experiments were done moderately at room temperature, and high yields in suitable times were obtained under these conditions.     

Oxidation of 1,4-Dihydropyridines under Mild and Heterogeneous Conditions

A combination of NaHSO₄.H₂O and NaNO₂ in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of dihydropyridines to their corresponding pyridine derivatives at room temperature with excellent yields.