Screening of several biological activities induced by different sesquiterpene lactones isolated from Centaurea behen L. and Rhaponticum repens (L.) Hidalgo

This study aims to evaluate the in vitro cytotoxic, in vitro and in ovo anti-angiogenic effects and antimicrobial activity of sesquiterpene lactones (SLs) from two plants Centaurea behen and Rhaponticum repens (L.). Five SLs, including cynaropicrin (1), 4β,15-dehydro-3-dehydrosolstitialin A (2), aguerin B (3), janerin (4), cebellin E (5), and a flavone hispidulin (6) were isolated from C. behen (compounds 1–3) and R. repens (compounds 4–6). Cynaropicrin (1) and aguerin B (3) were characterised by strong cytotoxic activities against A2780 cells with IC₅₀ values of 1.15 and 1.62 μg mL^?1, respectively, comparable to that of doxorubicin (IC₅₀ = 1.17 μg mL^?1). The anti-angiogenic study showed the remarkable inhibitory effect of cynaropicrin (1) and aguerin B (3) on the proliferation and migration of HUVECs. In addition, cynaropycrin and aguerin B exhibited significant angio-inhibitory effects in CAM assay. These findings may be useful for the development of novel chemotherapeutic agents for the treatment of cancer.     

Co(III) complexes of Me-salpn and Me-salbn and the ring size effect on the coordination modes and electrochemical properties: The crystal structures of trans-[Co(Me-salpn)(py)2]PF6 and cis-α-[Co(Me-salbn)(4-Mepy)2]BPh4 · 4-Mepy

The synthesis and characterization of a series of cobalt(III) complexes of the general type [Co(N₂O₂)(L₂)]⁺ are described. The N₂O₂ Schiff base ligands used are Me-salpn (H₂Me-salpn = N,N′-bis(methylsalicylidene)-1,3-propylenediamine) (1–3) and Me-salbn (H₂Me-salbn = N,N′-bis(methylsalicylidene)-1,4-butylenediamine) (4–5). The two ancillary ligands L include: pyridine (py) 1, 3-metheylpyridine (3-Mepy) 2, 1-methylimidazole (1-MeIm) 3, 4-methylpyridine (4-Mepy) 4 and pyridine (py) 5. These complexes have been characterized by elemental analyses, IR, UV–Vis, and ¹H NMR spectroscopy. The crystal structures of trans-[Co^III(Me-salpn)(py)₂]PF₆, 1, and cis-α-[Co^III(Me-salbn)(4-Mepy)₂]BPh₄ · 4-Mepy, 4, have been determined by X-ray diffraction. Examination of the solution and crystalline structures revealed that the outer coordination sphere of the complexes exerts a noticeable influence on the inner coordination sphere of the Co(III) ion. The electrochemical reduction of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Co^III–Co^II is electrochemically irreversible, which is accompanied by the dissociation of the axial (R-py)–cobalt bonds. It has also been observed that the Co(III) state is stabilized with increasing the flexibility of the ligand environment.     

Synthesis of novel symmetrical bis‐schiff bases of 5,5′‐methylenebis(2‐aminothiazole)

Novel symmetrical bis‐Schiff bases have been prepared cleanly and efficiently in the presence of formic acid catalyst in methanol from the reaction of symmetrical primary bis‐amine of 5,5′‐methylenebis(2‐aminothiazole) ( 1 ) and a series of aromatic aldehyde derivatives under mild conditions. The advantages of this reaction are simplicity of the reaction procedure, simple work‐up and pure products with high yields. The structures of all the new synthesized symmetrical bis‐Schiff bases were confirmed by elemental analyses, IR, ¹H‐NMR, ¹³C‐NMR and mass spectra.     

Nickel(II) Complexes with a Hydroxyl Pendant‐Armed Macrocyclic Ligand: Synthesis,Characterization, and Crystal Structures

The reactions of different nickel(II) salts with a mixed‐donor macrocyclic ligand L (6,7,8,9,10,11,18,19‐octahydro‐5H, 17H‐dibenzo[f,o][1,5,9,13] dioxadiazacyclohexadecin‐18‐ol), potentially pentadentate N₂O₃ donor sets containing one pendant alcohol function have been investigated. The physical properties and the chemical structures of 1:1 (metal:ligand) NiLX₂ (X = Cl^?, Br^?, NO₃^?, ClO₄^?) complexes have been characterized by using IR, UV‐Vis spectroscopy and conductance measurements. The X‐ray determination have been employed to probe the nature of the respective complexes in solid state. The nickel atom in [NiL(NO₃)]NO₃·0.5H₂O complex is six‐coordinate with a distorted octahedral coordination in which the all N₂O₃ donor atoms are coordinated to the nickel atom. The coordination sphere is completed by a nitrate anion. In contrast to the above nickel complex, in [NiLCl₂] complex the pendant hydroxyl arm of macrocycle remains uncoordinated and ligand acts as tetradentate N₂O₂ donor atoms. The coordination sphere is completed by two chloride anions and the nickel atom is six‐coordinate with a distorted octahedral coordination.     

Toward efficient functionalization of polystyrene backbone through ketene chemistry: Synthesis,characterization, and DFT study

In this study, polystyrene was functionalized with Meldrum's acid toward the introduction of the ketenes (CCO) system to its backbone for producing a dramatically reactive intermediate. Meldrum's acid, as a ketene source, was reacted by poly(styrene-co-p-chloromethyl styrene) through a simple nucleophilic reaction to synthesize poly(styrene-co-styryl Meldrum's acid). Then, the pendant Meldrum's acid under thermal treatment converted to ketene intermediate resulting in highly reactive polystyrenes derivatives, which rapidly reacted by nucleophilic reagents to afford ultimate organic building blocks. The polystyrene derivatives were characterized using elemental analysis, FT-IR, high-resolution solid-state NMR, thermogravimetric analysis (TGA), and differential thermogravimetric analysis (DTG). To clarify the evolutionary mechanisms of polystyrene products, density functional theory (DFT) method B3LYP with the 6–311++G(2d,p) basis set was used. We studied the preparation of polystyrene model compounds through Meldrum's acid thermolysis and nucleophilic substitution. The kinetic and thermodynamic parameters in all reactions and the structural and electronic properties of all molecules were calculated. These data exhibited that based on Gibbs Free energy values, the structure of syndiotactic polystyrene is more stable than that of isotactic polystyrene. Furthermore, it was found that the presence of an electron donor or acceptor substituent on the polystyrene structure affects the electronic bandgap.     

Exceptionally Stable Dimers and Trimers of Au25 Clusters Linked with a Bidentate Dithiol: Synthesis,Structure and Chirality Study

A bidentate chiral dithiol (diBINAS) is utilised to bridge Au₂₅ nanoclusters to form oligomers. Separation by size allows the isolation of fractions that are stable thanks to the bidentate nature of the linker. The structure of the products is elucidated by small-angle X-ray scattering and calculated using density functional theory. Additional structural details are studied by diffusion-ordered nuclear magnetic resonance spectroscopy, transmission electron microscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. Significant changes in the optical properties are analysed by UV/Vis and fluorescence spectroscopies, with the latter demonstrating a strong emission enhancement. Furthermore, the emergent chiral characteristics are studied by circular dichroism. Due to the geometry constraints of the nanocluster assemblies, diBINAS can be regarded as a templating molecule, taking a step towards the directed self-assembly of metal clusters.     

Analytical Model for CO2 Injection into Brine Aquifers-Containing Residual CH4

During CO₂ injection into brine aquifers-containing residual and/or dissolved CH₄, three distinct regions develop: (1) a single-phase, dry-out region around the well-bore filled with pure supercritical CO₂; (2) a two-phase, two-component system containing CO₂ and brine; and (3) a two-phase, two-component system containing CH₄, and brine. This article extends an existing analytical solution, for pressure buildup during CO₂ injection into brine aquifers, by incorporating dissolved and/or residual CH₄. In this way, the solution additionally accounts for partial miscibility of the CO₂?CCH₄?Cbrine system and the relative permeability hysteresis associated with historic imbibition of brine and current drainage due to CO₂ injection and CH₄ bank development. Comparison of the analytical solution results with commercial simulator, CMG-GEM, shows excellent agreement among a range of different scenarios. The presence of residual CH₄ in a brine aquifer summons two competing phenomena, (1) reduction in relative permeability (phase interference), which increases pressure buildup by reducing total mobility, and (2) increase in bulk compressibility which decreases pressure buildup of the system. If initial CH₄ is dissolved (no free CH₄), these effects are not as important as they are in the residual gas scenario. Relative permeability hysteresis increased the CH₄ bank length (compared to non-hysteretic relative permeability), which led to further reduction in pressure buildup. The nature of relative permeability functions controls whether residual CH₄ is beneficial or disadvantageous to CO₂ storage capacity and injectivity in a candid brine aquifer.     

Flow Field Around Single and Tandem Piers

The present study provides a comparison between the flow pattern around two circular piers in tandem and a single pier set up on a moderately rough flat bed in a laboratory flume. Velocities are measured by an Acoustic Doppler Velocimeter (ADV). The contours of the time-averaged velocity components, Reynolds shear stresses, turbulence intensities and turbulence kinetic energy at different planes are presented. Streamlines and vectors are used to study the flow features. The analysis of power spectra around the piers is also presented. The results show that the presence of downstream pier changes the flow structure to a great extent, particularly in the near-wake region. Within the gap between the two piers, a stronger and substantial upflow is shaped. However, a weaker transverse-deflection is formed in comparison with that in the single pier. Near the bed, the velocity of flow approaching the downstream pier decreases to 0.2–0.3 times of the approach mean velocity (U ₀) due to the sheltering effect of the upstream pier. In the wake of downstream pier, the flow structure is completely different from the one in the wake of single pier. In comparison with the single pier, the values of turbulence kinetic energy and turbulence intensities show a considerable decrease around the tandem piers. In tandem piers, the high values of turbulence characteristics are found near the downstream pier. There is a recirculation zones just upstream of the sheltered pier close to the bed and another behind that pier near the free surface. The results show a decrease in the strength of vortical structure in the wake of tandem piers in comparison with single pier. It is shown that the formation of flow with different Reynolds number along the flow depth due to the effect of bed roughness, as well as pier spacing, can influence the type of flow regime of tandem case. In addition to enhancing the flow structure indulgence, the present detailed measurements can also be used for verification of numerical models.     

Photocatalytic Degradation of Antibiotic Norfloxacin Aqueous Solution by Ce/Bi2WO6: Optimization and Simulation of Process by RSM

Russian Journal of Applied Chemistry - This study evaluated a removal efficiency of NLFX from aqueous solutions using a photocatalytic process. In this study, Bi2WO6 were synthesized by microwave...