Thermodynamic study of complex formation between 18-crown-6 and potassium ion in some binary non-aqueous solvents using a conductometric method

The complexation reaction between a macrocyclic polyether, 18-crown-6 (18C6), and potassium ion was studied in methanol (MeOH)-acetonitrile (AN), dimethylformamide (DMF)-AN and propylecarbonate (PC)-DMF binary solvent systems at different temperatures using a conductometric method. It was found that the stability of the 1:1 complex formed between K(+) ion and this ligand increases with decreasing temperature. Standard enthalpies and standard entropies of the complex formation were obtained from the temperature dependence of the stability constant. In all cases negative DeltaH(o)(c) and DeltaS(o)(c) values characterize the formation of 18C6-K(+) complex. The results obtained show that the stability of the complex is governed by the solvent medium and the thermodynamic parameters DeltaH(o)(c), DeltaS(o)(c) and DeltaG(o)(c) are sensitive to the composition of the mixed solvents. In addition, it was found that the stability constant of the resulting 1:1 complex among various neat solvents used varies in the order PC > MeOH > AN > DMF.     

Synthesis and Single Crystal Structure Characterization of Dinuclear and Polymeric Mixed-ligand Coordination Compounds of Zinc(II) and Cadmium(II) with the Bridging Ligand 1,2-Bis(pyridin-4-ylmethylene)hydrazine

Three d¹⁰-transition-metal coordination compounds [Cd(tfpb)₂(4-bpmh)]_n ( 1 ), [Cd(9-aca)(NO₃)(OHCH₃)(4-bpmh)]_n ( 2 ) and [Zn₂(dpp)₄(4-bpmh)] ( 3 ) with the bridging ligand 4-bpmh were synthesized [4-bpmh = 1,2-bis(pyridin-4-ylmethylene)hydrazine, tfpb = 4,4,4-trifluoro-1-phenylbutane-1,3-dionate, 9-aca = anthracene-9-carboxylate, dpp = 1,3-diphenylpropane-1,3-dionate]. Compounds 1 – 3 were characterized by FT-IR spectroscopy, elemental analysis, and structurally authenticated by X-ray crystallography. Compounds 1 – 3 are constructed by an O,O'-donor ligand including chelating β-diketonates (tfpb, dpp) in 1 and 3 and a carboxylate ligand (9-aca) in 2 in combination with a linear neutral bidentate and bridging N-ligand (4-bpmh). The assembly and action of the bridging 4-bpmh ligand leads to one-dimensional coordination polymers in 1 , 2 and to a dinuclear coordination complex in 3 . The structures and the solid-state supramolecular interactions for studying the crystal packing fashions of 1 – 3 were analyzed. The supramolecular interactions including hydrogen bonding, C–H ··· π, π ··· π, and C–F ··· π in 1 , 2 , and 3 were founded.     

Preparation and characterization of TiO<Subscript>2</Subscript> sol–gel modified nanocomposite films

In this study, the role of TiO₂ MT-150A loading in the polymeric sol was investigated for the synthesis of immobilized TiO₂ nanocomposite films on glass substrate using the MT-150A nanoparticles-modified sol–gel method. The nanocomposite film properties were examined using different material characterization techniques including X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, UV–Vis spectrophotometer, Scotch tape test and pencil hardness test. The hydrophilicity of films during UV/Vis irradiation and storage in a dark place were evaluated by a contact angle analyzer. The MT-150A loading had a significant effect on the amount of crystallite phases in the films. However, increasing the MT-150A loading in the sol resulted in an increase in rutile phase content. In addition, increasing MT-150A loading in the sol yielded films with higher hydrophilicity but a concentration of 10–30 g/L MT-150A in the sol was found as the maximum for obtaining films with good adherence on the glass substrate.     

Approximation of the Cubic Functional Equations in Lipschitz Spaces

Let G be an Abelian group and let ρ : G×G→[0,∞) be a metric on GLet E be a normed spaceWe prove that under some conditions if f : G→E is an odd function and Cx : G→E defined by Cx(y) := 2 f(x + y) +2 f(x-y) + 12 f(x)-f(2x + y)-f(2x-y)is a cubic function for all x∈G, then there exists a cubic function C : G→E such that f-C is LipschitzMoreover, we investigate the stability of cubic functional equation2 f(x + y) + 2 f(x-y) + 12 f(x)-f(2x + y)-f(2x-y) = 0 on Lipschitz spaces.     

The influence of gas flow rate on the structural,mechanical, optical and wettability of diamond-like carbon thin films

In this research, diamond-like carbon (DLC) thin films were deposited on silicon substrates by radio-frequency plasma enhanced chemical vapor deposition method using gas mixture of CH₄ and Ar. The effect of different CH₄/Ar gas ratio on the structure, refractive index, transmission and hardness of the DLC thin films were investigated by means of Raman spectroscopy, ellipsometry, Fourier transform Infrared Spectroscopy and nano-indentation methods, respectively. Nuclear resonant reaction analysis was used to measure the amount of hydrogen and carbon in the thin films. Furthermore, wettability of the thin films was achieved by measuring of water contact angle (WCA). The results indicated that the structural properties of the diamond-like carbon thin films are strongly dependent on the composition of gas mixture. Based on ellipsometry results, refractive index of the thin films varied in the range of 1.89–2.06 at 550 nm. FTIR results determined that deposition of DLC thin films on silicon substrate led to an increase of the light transmission in IR region and these films have the potential to be used in silicon optics as the antireflective coatings in this region. Nano-indentation analysis showed that the thin films hardness changed in the range of 7.5–11 GPa. On the other hand hydrogen content and fraction of C?H bonds in the samples increased by an increase in the gas ratio of CH₄/Ar. Also, WCA measurements indicated that WCA for thin films with gas ratio of 3/7 is the most and equal to 79°.     

Optical and electrical properties of aluminum zinc oxide (AZO) nanostructured thin film deposited on polycarbonate substrate

Transparent polymer materials, due to their unique properties, such as light weight, optical transparency, and electrical and mechanical properties, have become very attractive as a replacement for inorganic glass substrates in a wide range of optoelectronic applications. In this research, aluminum zinc oxide nanostructured thin film was deposited on polycarbonate polymer substrates using a magnetron sputtering technique. The structure, morphology, and surface composition of the thin film were investigated by X-ray diffraction and field emission scanning electron microscopy. The optical and electrical properties of the thin film were investigated by UV–VIS-NIR spectrophotometer, ellipsometer, and four point probe method. The X-ray diffraction pattern showed that the aluminum zinc oxide thin film had a polycrystalline structure. The optical and electrical results indicated that the refractive index, band gap, and sheet resistance of the aluminum zinc oxide thin film were 1.8, 3.2 eV, and 265 Ω/sq, respectively.     

Optical and hydrophilic properties of Cr doped TiO2-SiO2 nanostructure thin film

Cr doped TiO₂-SiO₂ nanostructure thin film on glass substrates was prepared by a sol-gel dip coating process. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structural and chemical properties of the films. A UV-vis spectrophotometer was used to measure the transmittance spectra of the thin film. The hydrophilicity of the thin film during irradiation and storage in a dark place was measured by a contact angle analyzer. The results indicated that Cr doping has a significant effect on the transmittance and super-hydrophilicity of TiO₂-SiO₂ thin film.     

New mononuclear copper(II) complexes from β-diketone and β-keto ester N-donor heterocyclic ligands: structure,bioactivity, and molecular simulation studies

Four new mononuclear copper(II) complexes with methyl acetoacetate and benzoylacetone in the presence of 1,10-phenanthroline and 2,2′-bipyridine were synthesized and characterized by elemental analyses, FT-IR, and UV–Vis spectroscopy. The molecular structures of complexes [Cu(MAA)(bpy)(ClO₄)] (1a), [Cu(bzac)(bpy)]ClO₄ (2a), [Cu(MAA)(phen)(ClO₄)] (1b) and [Cu(bzac)(phen)(ClO₄)] (2b) were determined by single crystal X-ray diffraction technique. 1a, 1b, and 2b are five coordinate with a distorted square pyramidal geometry and the structure of 2a consists of isolated [Cu(bzac)(bpy)]⁺ cations and perchlorate counter anions. The electrochemical studies of copper complexes in acetonitrile solution showed that Cu^II/Cu^I reduction processes are electrochemically irreversible. Cytotoxic activity of complexes was screened, including an MTT assay against gastric cancer cell line (MKN-45). The four Cu(II) complexes exhibited lethal effects against MKN-45 cell lines and the half maximal inhibitory concentration (IC₅₀) values obtained were much lower in comparison with 5-fluorouracil. In addition, MTT and migration studies revealed that benzoylacetone complexes are more active than complexes of methyl acetoacetate against the MKN-45 cancer cell lines. Docking simulations of Cu(II) complexes on DNA revealed that the most stable adducts with DNA bind in the minor groove. All complexes display a binding specificity to the A/T rich regions.     

Practical and efficient synthesis of tetrahydrobenzo[<Emphasis Type="Italic">b</Emphasis>]pyran using caffeine supported on silica as an ionic liquid solid acid catalyst

The new catalyst silica-caffeine hydrogen sulfate [SiO₂-caff.]HSO₄ was conveniently prepared from commercially available 3-chloropropyltriethoxysilane via immobilization on silica followed by reaction with caffeine. The catalyst prepared was then characterized by the FT-IR spectroscopy, TGA, EDX, and SEM techniques. It was found that this heterogeneous catalyst was a highly efficient one for the synthesis of tetrahydrobenzo[b]pyrans in good-to-high yields, and could be recovered by a simple filtration of the reaction solution and reused for five consecutive runs. The attractive features of this method are simple procedure, clean reaction, easy work-up, use of a reusable catalyst, and performing a multi-component reaction.     

Thermal analysis of high-index-contrast grating (HCG)-based VCSEL

A 3-D thermal analysis of 870 nm high-index-contrast grating (HCG)-based vertical cavity surface emitting laser (VCSEL) by using finite volume method (FVM) is presented in this paper. The HCG-based VCSEL is modeled by applying a steady-state 3-D heat dissipation model. Temperature distribution profile and thermal resistance (R_th) of the device are investigated by inserting the heat source value into the thermal simulation. Also, this analysis is performed for a conventional VCSEL operating at the same wavelength and under the same injected current as well as the same geometric sizes. The analysis shows that the maximum temperature inside the HCG-based VCSEL is lower than that inside the conventional VCSEL.