Calorimetric study of melts in the System KF - K<Subscript>2</Subscript>NbF<Subscript>7</Subscript>

The relative enthalpies of melts in the system KF - K₂NbF₇ were measured by drop-calorimetry at the temperatures 1058, 1140 and 1208 K as a function of composition. Heat capacities of melted mixtures and enthalpies of mixing were determined using the experimental data. The molar heat capacity of melts diverges slightly from additivity. The molar enthalpy of mixing of melts shows small negative deviation from ideality which decreases with decreasing temperature. The thermal effect at mixing was assigned predominantly to association reactions producing more complex fluoroniobate anions.      

2-pyrrolidone - capped Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocrystals

Water-soluble Mn₃O₄ nanocrystals have been prepared through thermal decomposition in a high temperature boiling solvent, 2-pyrrolidone. The final product was characterized with XRD, SEM, TEM, FTIR and Zeta Potential measurements. Average crystallite size was calculated as ∼15 nm using XRD peak broadening. TEM analysis revealed spherical nanoparticles with an average diameter of 14±0.4 nm. FTIR analysis indicated that 2-pyrrolidone coordinates with the Mn₃O₄ nanocrystals only via O from the carbonyl group, thus confining their growth and protecting their surfaces from interaction with neighboring particles.      

Methylcellulose/SiO<Subscript>2</Subscript> hybrids: sol-gel preparation and characterization by XRD,FTIR and AFM

Methylcellulose (MC) / SiO₂ organic / inorganic hybrid materials have been prepared from MC and methyltriethoxysilane or ethyltrimethoxysilane, and characterized by XRD, FTIR and AFM. XRD showed peak shifts. FTIR shows intermolecular hydrogen bonding between MC and SiO₂. AFM depicts surface roughness which depends on the silica precursor and MC content.      

Determination of europium by using the chemical oscillating system of Ce(IV)-KBrO<Subscript>3</Subscript>-acetone-oxalic acid-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>

A sensitive and convenient method for the determination of trace europium ions using an oscillating chemical reaction involving Ce(IV) - KBrO₃ - acetone - oxalic acid - H₂SO₄ was proposed. The results indicated that the changes in oscillating period (T) was linearly proportional to the negative logarithmic concentration of Eu³⁺ (-log C) in the range of 1.41 × 10⁻⁸ ˜ 1.41 × 10⁻⁴ mol L⁻¹ (r = 0.9982) with a detection limit of 1.04 × 10⁻⁹ mol L⁻¹. The recoveries were limited to the range of 99.5% to 100.8%. Under the same conditions, other rare earth ions did not interfere with the determination of Eu³⁺. In addition, a perturbation mechanism was also discussed briefly.      

Effect of the polymeric coating over Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> particles used for magnetic separation

In this work, the synthesis of magnetite nanoparticles by two variant chemical coprecipitation methods that involve reflux and aging conditions was investigated. The influence of the synthesis conditions on particle size, morphology, magnetic properties and protein adsorption were studied. The synthesized magnetite nanoparticles showed a spherical shape with an average particle size directly influenced by the synthesis technique. Particles of average size 27 nm and 200 nm were obtained. When the coprecipitation method was used without reflux and aging, the smallest particles were obtained. Magnetite nanoparticles obtained from both methods exhibited a superparamagnetic behavior and their saturation magnetization was particle size dependent. Values of 67 and 78 emu g⁻¹ were obtained for the 27 nm and 200 nm magnetite particles, respectively. The nanoparticles were coated with silica, aminosilane, and silica-aminosilane shell. The influence of the coating on protein absorption was studied using Bovine Serum Albumin (BSA) protein.      

Synthesis of dibromo ketones by the reaction of the environmentally benign H<Subscript>2</Subscript>O<Subscript>2</Subscript>-HBr system with oximes

It was found that oximes undergo deoximation in the presence of the H₂O_2aq-HBr_aq system to form ketones and bromo ketones. This reaction provided the basis for the synthesis of dibromo ketones in yields varying from 40% to 94%. This method is environmentally friendly, sustainable, and easy to perform. The results of this investigation extend the potential of the use of oximes for the protection of carbonyl group, thus offering the ability to perform not only conventional deoximation but also the subsequent bromination of ketones. The reaction is easily scaled up and dibromo ketones can be prepared in gram amounts.      

The crystal structure of Ho<Subscript>4</Subscript>Ni<Subscript>11</Subscript>In<Subscript>20</Subscript>

The polycrystalline Ho₄Ni₁₁In₂₀ was obtained by arc-melting of the elements. The subsequent high temperature procedure was used for single crystal growth. Crystal structure of the compound was investigated by X-ray single crystal method: U₄Ni₁₁Ga₂₀ type, C 2/m, a = 22.4528(17), b = 4.2947(3), c = 16.5587(13) Å, β = 124.591(5)°, R1 = 0.0276, wR2 = 0.0493 for 1989 independent reflections with [I>2σ(I)].The structure is composed of three-dimensional network from Ni and In atoms in which Ho atoms fill distorted pentagonal channels. Open image in new window     

Controlled synthesis,characterization and thermal properties of Mg<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>5</Subscript>

Optimum conditions for synthesizing monoclinic and triclinic Mg₂B₂O₅ compounds by high-temperature solid-state reactions were investigated. Mixtures composed of boric acid and magnesium oxide at MgO:B₂O₃ mole ratios of 1:0.25, 1:0.5 and 1:1.5 were heated for 1 hour at temperatures between 600–1050°C and the formed phases were identified by XRD analysis. Monoclinic Mg₂B₂O₅ was formed by heating at 850°C for 4 hours together with minimum amounts of triclinic Mg₂B₂O₅, while triclinic Mg₂B₂O₅ was formed as a single phase at 1050°C for the same reaction time. The products obtained at optimum conditions were subjected to a series of tests to determine their chemical compositions, particle size distributions, surface area values, IR spectra and TG/DTA patterns.      

Removal of cadmium and copper ions by <Emphasis Type="Italic">Trichosporon cutaneum</Emphasis> R57 cells immobilized onto polyvinyl alcohol/tetraethoxysilane hybrid matrices

Polyvinyl alcohol (PVA) and tetraethoxysilane (TEOS) hybrid materials were prepared by sol-gel methods and tested as matrices for immobilization of Trichosporon cutaneum R57, capable of removing cadmium and copper ions from aqueous solutions. A kinetic model was applied and the effects of matrix TEOS content on the copper and cadmium uptake equilibria and rate constants were investigated.      

Simultaneous displacement of a nitro group during coupling of diazotized <Emphasis Type="Italic">o</Emphasis>-nitroaniline with phenols

During the diazo-coupling reaction, nucleophilic displacement of a nitro group was also observed. This was the main reaction (1→7) when the starting amine bore either a chlorine or methoxy group at the para position (1b–c). The newly prepared compounds (7) might serve as convenient building blocks in synthesis of some heterocycles.      

Molecular dynamics simulation study of the diamond D<Subscript>5</Subscript> substructures

Diamond D₅ is the name proposed by Diudea for hyper-diamonds having their rings mostly pentagonal. Within D₅, in crystallographic terms: the mtn structure, known in clathrates of type II, several substructures can be defined. In the present work, the structural stability of such intermediates/fragments appearing in the construction/destruction of D₅ net was investigated using molecular dynamics simulation. Calculations were performed using an empirical many-body potential energy function for hydrocarbons. It has been found that, at normal temperature, the hexagonal hyper-rings are more stable while at higher temperature, the pentagonal ones are relatively more resistant against heat treatment.      

Influence of ThO<Subscript>2</Subscript> on the photocatalytic activity of TiO<Subscript>2</Subscript>

Microcomposites consisting of TiO₂ (or Ce-doped TiO₂) and ThO₂ (0.5–2% of the TiO₂ mass) are produced by sol-gel synthesis of TiO₂ in presence of ThO₂. X-ray diffraction study reveals the effects of ThO₂ (compared to the ThO₂-free TiO₂, obtained by the same method) on the anatase interplanar distances, crystallites size and phase composition. The photocatalytic tests in presence of the composites under UV irradiation reveal an increase of the Malachite Green degradation rate constant. The effect depends on the Th relative content, temperature of annealing of the catalyst and addition of other doping agent. The highest photocatalytic activity is observed for TiO₂ obtained at 550°C and containing 1% ThO₂. The composite exhibits activity in dark, also. The presence of Ce⁴⁺ ions is not an obligatory requirement for the realization of the ThO₂ effect. The reported results suggest that the radioactivity of the Th and/or its decay products is one of the main factors responsible for the increased photocatalytic activity of TiO₂.      

Efficient and solvent-free synthesis of 1-amidoalkyl-2-naphthols using <Emphasis Type="Italic">N,N,N’,N’</Emphasis>-tetrabromobenzene-1,3-disulfonamide

N,N,N,’N’-Tetrabromobenzene-1,3-disulfonamide [TBBDA] is found to be a reusable catalyst for efficient synthesis of various amidoalkyl naphthols from β-naphthol, aromatic aldehydes and urea in good to high yields under solvent-free conditions.      

N-hexylpyridinium bis(trifluoromethylsulfonyl)imide and Lewis acids — catalytic systems for Diels-Alder reaction

A comparative study of the Diels-Alder reactions between cyclopentadiene (1) and dienophiles (2 a–c) in N-hexylpyridinium bis(trifluoromethylsulfonyl)imide in a temperature range of 20–45°C is reported. The reaction rate constants and activation energies were calculated. Moreover, the catalytic systems based on N-hexylpyridinium bis(trifluoromethylsulfonyl)imide and Lewis acids were tested as a reaction media to perform the Diels-Alder reaction. Yb, Y, Mg, Zn triflates and chlorides (0.005 to 0.1 mmol) were used as catalysts. The recycling of catalytic system consisted of YCl3 and ionic liquid was performed.      

Toxic elements content in PM<Subscript>10</Subscript> samples from a coastal area of the Northern Adriatic Sea

PM₁₀ samples were collected during winter and summer seasons at two different sites in the area of Trieste (Italy). The content of As, Cd, Cr, Mn, Ni, Pb and V in the PM₁₀ samples was determined by inductively coupled plasma-mass spectrometry, with the purpose of evaluating the relevance of PM₁₀ inhalation as a route of human exposure to these elements. The results showed that the ambient air concentration of the aforementioned elements were below the limits or target values for both sites and season. Site and season-specific correlation analysis was conducted for the identification of metals with similar origin: very good correlation for the couple Ni-V was found in both sites and seasons, showing the influence of combustion of heavy oils in PM₁₀ composition. The inter-site and seasonal variability of both PM₁₀ and metal concentrations were examined. A stronger impact by the vehicular traffic on the PM₁₀ and metal concentrations was found for the urban site in both seasons. Because of the great importance of the “Bora” wind on the local climate, variability of PM₁₀ and toxic elements concentration with wind were analysed, allowing determination of the effect of wind on dilution of the pollutants for the urban site during both seasons.      

Synthesis of SnO<Subscript>2</Subscript> nanopowders by a sol-gel process using propanol-isopropanol mixture

A simple sol-gel process is proposed for synthesizing SnO₂ nanopowders utilizing normal propanol and isopropanol mixture instead of just using normal alcohols such as ethanol, propanol or butanol for Sol preparation. No surfactant was used in this Sol preparation process. The structure of sol is studied by FT-IR-ATR technique. On altering propanol to isopropanol ratio, three different nanopowders were obtained. X-ray powder diffraction, high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction pattern (SAED) and BET techniques were used to characterize prepared powders. Results show that smaller grain size was obtained via altering alcohols ratio. In addition, Merck commercial SnO₂ powder was also used as a reference material for comparing purposes; because it has nanometer scale (ca. 60 nm). HRTEM images show that obtained nanopowders were polycrystalline and their average diameters fall into the range of 6–80 nm. Finally, the effect of alkoxide ligand size through sol-gel synthesis on product particle size is discussed.      

Protolytic properties of the structurally rigid analogs of 2,6-distyrylpyridine. Widening the pH sensitivity range by the photochemical E→Z isomerisation and introduction of substituents capable to protolytic interactions

Protolytic interactions in the series of prospective fluorescent ratiometric wide-range pH indicators — structurally rigid analogs of 2,6-distyrylpyridine — (3E,5E)-3,5-dibenzylidene-8-phenyl-1,2,3,5,6,7-hexahydrodicyclopentano[b,e]pyridine — were investigated. The pyridine nitrogen atom basicity in these compounds is significantly lower in comparison with that of unsubstituted heterocycle and 2,6-distyrylpyridine. The photochemical E→Z photoisomerization and the side benzene rings substituents influence on the acid-base equilibria were studied. The complex multi-stage mechanism of the acid-base interactions of the polysubstituted compounds was elucidated. The most significant spectral effects were typical to the N,N-dialkylamino substituted compounds of the investigated series. The widest pH sensitivity interval covering nearly the full range of 0–14 units was demonstrated for compounds with both proton donor and proton acceptor substituents.      

Use of pyridinium ionic liquids as catalysts for the synthesis of 3,5-bis(dodecyloxycarbonyl)-1,4-dihydropyridine derivative

The synthesis of cationic amphiphilic 1,4-dihydropyridine derivative, potential gene delivery agent is achieved via an efficient multi-step sequence. The key step of this approach is a two-component Hantzsch type cyclisation of 3-oxo-2-[1-phenylmethylidene]-butyric acid dodecyl ester and 3-amino-but-2-enoic acid dodecyl ester utilising bis(2-hydroxyethyl)ether as a solvent and 1-butyl-4-methylpyridinium chloride as a catalyst. The 1,4-dihydropyridine derivative with long alkyl ester chains at positions 3 and 5 of the 1,4-DHP ring — 3,5-bis(dodecyloxycarbonyl)-2,6-dimethyl-4-phenyl-1,4-dihydropyridine was obtained in substantially higher yield with respect to classical Hantzsch synthesis. Bromination of this compound followed by nucleophilic substitution of bromine with pyridine gave the desired cationic amphiphilic 1,4-dihydropyridine.      

Kinetics and thermodynamics of adsorption of congo red on cellulose

Thermodynamics and kinetics of adsorption of congo red (CR) on cellulose are studied at 308–328 K. In the used concentration range of CR, interaction of CR with cellulose is exothermic and CR molecules adsorb chemically on cellulose surface. The effects of contact time, temperature and initial concentration of CR on kinetics of its adsorption on cellulose were investigated. The process proceeds according to the pseudo-second-order equation. Initial adsorption rate of adsorption is first-order in CR and the intraparticle diffusion of CR molecules within cellulose is identified as the main rate-limiting step.