Synthesis,X-ray crystal structure and DFT studies of cobalt(II) and vanadium(V) complexes with N,N,O-tridentate aroyl-hydrazone based ligand

A new aroyl-hydrazone, 2-pyridine carboxaldehyde-derived hydrazone ligand and its cobalt(II) (1) and vanadium(V) (2) complexes were prepared. The structures of these compounds were investigated using elemental analysis, spectral (IR, UV), and X-ray diffraction measurements. The electrochemical properties of the complexes were studied by cyclic voltammetry. The hydrazone ligand acted as tridentate and coordinated to vanadium and cobalt via N-imine, N-pyridine, and O-benzohydrazide atoms. The Co(II) complex crystallizes in the monoclinic system, space group P2₁/c, and has a binuclear structure. Chloride ions behave as the linking bridge and a tridentate hydrazine ligand HL and water as the terminal capping ligands. The central Co(II) ion has distorted octahedral geometry. The vanadium(V) complex crystallizes in the monoclinic crystal system, space group P2₁/n, and can be described as having highly distorted trigonal-bipyramidal coordination. The geometries and electronic properties of the complexes were also obtained using DFT and TD-DFT calculations.     

C-H activation in bithiazole ring with thallium(III) ion

Two novel organometallic complex of 2,2′-dimethyl-4,4′-bithiazole (dm4bt) ligand (L) with formula [Tl(dm4bt)₂(NO₃)(H₂O)] (1) and [Tl(dm4bt)₂(NO₃)(DMSO)] (2) have been synthesized and structurally characterized by elemental analysis, FT-IR, ¹H NMR spectra and X-ray crystallography. These complexes also display the first transoid conformation in bithiazole ligands in which C-H bond activation in bithiazole ring is observed with Tl(III) ion.     

Correlation between macrovoid formation and the ternary phase diagram for polyethersulfone membranes prepared from two nearly similar solvents

The morphological structure of membranes prepared from two nearly similar systems consisting of water/N,N-dimethylacetamide (DMAc)/polyethersulfone (PES) and water/N-methyl-2-pyrrolidone (NMP)/polyethersulfone (PES) has been studied. The morphology of the prepared membranes showed that both systems exhibit an instantaneous liquid–liquid demixing that leads to the formation of macrovoids in the resulting structures. Nevertheless, the resulting macrovoid structures were contrary to the generally accepted concepts concerning macrovoid formation. The membranes morphologies showed that in spite of better miscibility between water and DMAc, which must promote the formation of channel- and finger-like structures, more sponge-like structures were observed in membranes prepared from the water/DMAc/PES system compared to those prepared from the water/NMP/PES system. To find the source of this unexpected phenomenon, the complete ternary phase diagrams consisting of theoretical binodal curves, vitrification boundaries, and gelation boundaries were constructed for both systems and it was shown that gelation process occurs earlier in the water/DMAc/PES system compared to the other system, which inhibits the growth of macrovoids in this system.     

Fluidized-bed Fenton-like oxidation of a textile dye using natural magnetite

Degradation of Acid Orange 7 (AO7) as a model azo dye was investigated in a recirculating pilot fluidized-bed reactor by a Fenton-like process using natural magnetite (NM) and potassium persulfate (K₂S₂O₈). Scanning electron microscopy was performed to characterize the magnetite sample. The heterogeneous Fenton-like process (NM/\({\text{S}}_{2} {\text{O}}_{8}^{2 - }\)) is a modified method owing to its enhanced mass transfer. It can be operated reliably and simply by reducing the produced iron oxide sludge in the conventional Fenton process. Degradation efficiency (DE %) of AO7 by NM/ \({\text{S}}_{2} {\text{O}}_{8}^{2 - }\) process was affected by operational parameters. The DE % of 75 % was obtained for the AO7 treatment (15 mg/L) at the desired conditions, such as pH 5, 0.2 mM \({\text{S}}_{2} {\text{O}}_{8}^{2 - }\), and 0.5 g/L NM after 120 min of reaction time. The dye degradation rate in all the experiments followed the pseudo-second-order kinetic with high correlation coefficients (R ² ≥ 0.98). The low released iron concentration, successive reusability at milder pH and the recirculation mode with the proper mixing are the significant advantages of the NM/\({\text{S}}_{2} {\text{O}}_{8}^{2 - }\) process.     

Electrochemical and photo-assisted electrochemical treatment of the pesticide imidacloprid in aqueous solution by the Fenton process: effect of operational parameters

Research on Chemical Intermediates - The aim of this study was to compare the degradation efficiency (DE%) of imidacloprid as a model pesticide by electro-Fenton (EF) and photoelectro-Fenton...     

Poly(<Emphasis Type="Italic">n</Emphasis>-octyl methacrylate) viscosity index improver: Kinetic study via on-line <Superscript>1</Superscript>H-NMR technique

The free radical solution polymerization of n-octyl methacrylate has been studied in benzene-d ₆ in the presence of 2,2′-azobisisobutyronitrile as thermal initiator. An on-line nuclear magnetic resonance spectroscopy was applied to record the reaction data and to determine the monomer conversion at different times during the polymerization reaction. Effect of monomer and initiator concentration as well as reaction temperature on polymerization rate was studied. The order of the reaction with respect to initiator (0.45) was consistent with the classical kinetic rate equation, while the order of reaction with respect to monomer (1.87) was much greater than unity. An overall activation energy (E _a = 53.8 kJ/mol) was obtained over the temperature range 328?338 K. Also, the efficiency of the synthesized poly(n-octyl methacrylate) for improving the viscosity index of the lube oil was investigated.     

Irreversible electrowetting on thin fluoropolymer films

A study was conducted to investigate electrowetting reversibility associated with repeated voltage actuations for an aqueous droplet situated on a silicon dioxide insulator coated with an amorphous fluoropolymer film ranging in thickness from 20 to 80 nm. The experimental results indicate that irreversible trapped charge may occur at the aqueous-solid interface, giving rise to contact angle relaxation. The accumulation of trapped charge was found to be related to the applied electric field intensity and the breakdown strength of the fluoropolymer. On the basis of the data, an empirical model was developed to estimate the amount of trapped charge in the fluoropolymer as well as the voltage threshold for the onset of irreversible electrowetting.     

Über Umlagerungen bei der Cyclialkylierung von Arylpentanolen zu 2,3‐Dihydro‐1H‐inden‐Derivaten, 4. Mitteilung

On Rearrangements by Cyclialkylations of Arylpentanols to 2,3‐Dihydro‐1 H ‐indene Derivatives. Part 4. The Acid‐Catalyzed Cyclialkylation of 2,4‐Dimethyl‐2‐phenyl[3‐ ¹³ C]pentan‐3‐ol The cyclialkylation of 2,4‐dimethyl‐2‐phenyl[3‐¹³C]pentan‐3‐ol ( 4 ) gives only 2,3‐dihydro‐1,1,2,3‐tetramethyl‐1H‐[3‐¹³C]indene ( 6 ) (cf. Scheme 2) and not a trace of the isotopomeric 2,3‐dihydro‐1,1,2,3‐tetramethyl‐1H‐[2‐¹³C]indene ( 5 ). The mechanism proposed in [3] for the cyclialkylation of 4 (cf. Scheme 2, Path A) has, therefore, to be abandoned. The mechanism of Scheme 2, Path B, is proposed and may be considered as definitively established.     

K-Carrageenan Stimulates Pre-Osteoblast Proliferation and Osteogenic Differentiation: A Potential Factor for the Promotion of Bone Regeneration?

Current cell-based bone tissue regeneration strategies cannot cover large bone defects. K-carrageenan is a highly hydrophilic and biocompatible seaweed-derived sulfated polysaccharide, that has been proposed as a promising candidate for tissue engineering applications. Whether κ-carrageenan can be used to enhance bone regeneration is still unclear. In this study, we aimed to investigate whether κ-carrageenan has osteogenic potential by testing its effect on pre-osteoblast proliferation and osteogenic differentiation in vitro. Treatment with κ-carrageenan (0.5 and 2 mg/mL) increased both MC3T3-E1 pre-osteoblast adhesion and spreading at 1 h. K-carrageenan (0.125–2 mg/mL) dose-dependently increased pre-osteoblast proliferation and metabolic activity, with a maximum effect at 2 mg/mL at day three. K-carrageenan (0.5 and 2 mg/mL) increased osteogenic differentiation, as shown by enhanced alkaline phosphatase activity (1.8-fold increase at 2 mg/mL) at day four, and matrix mineralization (6.2-fold increase at 2 mg/mL) at day 21. K-carrageenan enhanced osteogenic gene expression (Opn, Dmp1, and Mepe) at day 14 and 21. In conclusion, κ-carrageenan promoted MC3T3-E1 pre-osteoblast adhesion and spreading, metabolic activity, proliferation, and osteogenic differentiation, suggesting that κ-carrageenan is a potential osteogenic inductive factor for clinical application to enhance bone regeneration.     

Damped vibration of a graphene sheet using a higher-order nonlocal strain-gradient Kirchhoff plate model

A higher-order nonlocal strain-gradient model is presented for the damped vibration analysis of single-layer graphene sheets (SLGSs) in hygrothermal environment. Based on Kirchhoff plate theory in conjunction with a higher-order (bi-Helmholtz) nonlocal strain gradient theory, the equations of motion are obtained using Hamilton's principle. The higher-order nonlocal strain gradient theory has lower- and higher-order nonlocal parameters and a material characteristic parameter. The presented model can reasonably interpret the softening effects of the SLGS, and indicates a reasonably good match with the experimental flexural frequencies. Finally, the roles of viscous and structural damping coefficients, small-scale parameters, hygrothermal environment and elastic foundation on the vibrational responses of SLGSs are studied in detail.