Kinetics and solvent effects in the acid hydrolysis of potassium ethyl malonate in dioxane-water and acetone-water mixtures

The acid-catalysed hydrolysis of potassium ethyl malonate in presence of 0.05N-HCl in water and in dioxane-water as well as acetone-water mixtures containing up to about 90% by weight of the organic solvent was studied over the temperature range 30–55°C. The reaction rate decreases continuously with decreasing water content of the solvent mixtures until it reaches a minimum at about 80% dioxane and increases again. The isocomposition activation energy shows only slight changes with solvent composition. The kinetics of the reaction was investigated from the viewpoints of solvent composition, water concentration and dielectric constant. The radii and thermodynamic parameters of the activated complex were calculated and discussed. The conclusions drawn show that the reaction is better treated as an ion-dipole rather than an ion-ion interaction.With 1 Figure     

The Behavior of 3,3-Diphenylindan-1,2-dione Towards Phosphonium Ylides

The reaction of alkoxycarbonyl- and cyanomethylene(triphenyl)phosphoranes with 3,3-diphenylindan-1,2-dione in dry benzene at room temperature for about 5 h led to the formation of a mixture of (E)- and (Z)-diastereomers. On the other hand, treatment of the dione with acetylmethylene(triphenyl)phosphorane afforded a mixture of (E)-3,3-diphenyl-1-(2-oxo-2-methylethylidene)indan-2-one and unexpected product (E)-3-(3,3-diphenyl-2-oxoindan-1-ylidene)-4-(triphenyl-λ⁵-phosphanylidene)hexane-2,5-dione, whereas with benzoylmethylene(triphenyl)phosphorane gave a mixture of (E)-3,3-diphenyl-1-(2-oxo-2-phenylethylidene)indan-2-one, [(2R ^*,3S ^*)-3-benzoyl-8,8-diphenyl-3,8-dihydro-2H-indeno{2,1-b}furan-2-yl]phenylmethanone and 1,4-diphenyl-2-(3,3-diphenyl-2-hydroxy-3H-inden-1-yl)but-2-ene-1,4-dione. The reaction mechanisms are considered and structural assignments of the new compounds are based on spectroscopic evidence. The molecular structures of the two diastereomers and the unexpected product were elucidated by X-ray crystallography.     

Kinetics and thermodynamics studies of copper exchange on Na-montmorillonite clay mineral

The kinetics of Cu ion exchange on Na-montmorillonite clay has been investigated at 20, 30, and 40 degrees C in water, methanol, and ethanol. The reaction is endothermic in nature. Solvent effects on the reaction rate have been discussed. The thermodynamic activation parameters were calculated and discussed in terms of solvation effects. A multiple reaction rate order equation was used to describe the adsorption process. Lower rates and higher activation energies (Ea) were observed in aqueous solution than in either of the alcohols. The Ea values ranged from 20.88 kJmol(-1) in water to 9.20 kJmol(-1) in ethanol, while at 20 degrees C the rate constant (k) varied from 0.111 ppm(-1)s(-1) in water to 0.205 ppm(-1)s(-1) in ethanol. The main factor influencing the rate of the adsorption process is the mobility of the adsorbed Cu cations, which is apparently larger in alcohols than in water, due to the difference in the molar activation energy of the solvent. The determined isokinetic temperature indicates that the reaction is enthalpy-controlled, where the interaction between solvent and clay surface plays an important role. A reaction mechanism that describes the solvent effect on the rate of Cu ion exchange is proposed.     

Comparative validated chromatographic methods for the simultaneous determination of caffeine,codeine, paracetamol along with the related compound " p-aminophenol"="" in="" tablets"="

JPC – Journal of Planar Chromatography – Modern TLC - This paper presents two validated chromatographic methods, namely thin-layer chromatography (TLC)–densitometry and...     

Nomad Jellyfish Rhopilema nomadica Venom Induces Apoptotic Cell Death and Cell Cycle Arrest in Human Hepatocellular Carcinoma HepG2 Cells

Jellyfish venom is a rich source of bioactive proteins and peptides with various biological activities including antioxidant, antimicrobial and antitumor effects. However, the anti-proliferative activity of the crude extract of Rhopilema nomadica jellyfish venom has not been examined yet. The present study aimed at the investigation of the in vitro effect of R. nomadica venom on liver cancer cells (HepG2), breast cancer cells (MDA-MB231), human normal fibroblast (HFB4), and human normal lung cells (WI-38) proliferation by using MTT assay. The apoptotic cell death in HepG2 cells was investigated using Annexin V-FITC/PI double staining-based flow cytometry analysis, western blot analysis, and DNA fragmentation assays. R. nomadica venom displayed significant dose-dependent cytotoxicity on HepG2 cells after 48 h of treatment with IC₅₀ value of 50 μg/mL and higher toxicity (3:5-fold change) against MDA-MB231, HFB4, and WI-38 cells. R. nomadica venom showed a prominent increase of apoptosis as revealed by cell cycle arrest at G2/M phase, upregulation of p53, BAX, and caspase-3 proteins, and the down-regulation of anti-apoptotic Bcl-2 protein and DNA fragmentation. These findings suggest that R. nomadica venom induces apoptosis in hepatocellular carcinoma cells. To the best of the authors’ knowledge, this is the first scientific evidence demonstrating the induction of apoptosis and cell cycle arrest of R. nomadica jellyfish venom.     

Some dielectric properties of novel nano‐s‐triazine derivatives

The evaluation of the dielectric properties of s‐triazine and its mono‐, di‐, tri‐(trityloxy)triazine derivates as a function of temperature from room temperature to 200°C, and frequency varying from 50 Hz to 5 MHz was performed. The dielectric constant increases with the increase of both temperature and frequency. Moreover, from the measured dielectric loss ε″ we found that there are different types of electric energy losses in the presence of an alternating electric field from which we calculate the entropy ΔS and the enthalpy change ΔH of the dielectric relaxation for each sample. The dielectric relaxation was attributed to the phase transition of the s‐triazine derivatives. Additionally, ac‐electrical conductivity as a function of frequency at different temperatures were studied. Analysis of ac conductivity data indicates that the correlated barrier hopping model is the most suitable mechanism for the ac‐conductance behavior. X‐ray diffraction and scanning electron microscopy were performed on the compounds under consideration to determine the grain size of each sample, which was found in the range of 3 to 100 nm.     

Biosynthesis and Characterization of Extracellular Silver Nanoparticles from Streptomyces aizuneusis: Antimicrobial,Anti Larval,and Anticancer Activities

The ability of microorganisms to reduce inorganic metals has launched an exciting eco-friendly approach towards developing green nanotechnology. Thus, the synthesis of metal nanoparticles through a biological approach is an important aspect of current nanotechnology. In this study, Streptomyces aizuneusis ATCC 14921 gave the small particle of silver nanoparticles (AgNPs) a size of 38.45 nm, with 1.342 optical density. AgNPs produced by Streptomyces aizuneusis were characterized by means of UV-VIS spectroscopy and transmission electron microscopy (TEM). The UV-Vis spectrum of the aqueous solution containing silver ion showed a peak between 410 to 430. Moreover, the majority of nanoparticles were found to be a spherical shape with variables between 11 to 42 nm, as seen under TEM. The purity of extracted AgNPs was investigated by energy dispersive X-ray analysis (EDXA), and the identification of the possible biomolecules responsible for the reduction of Ag⁺ ions by the cell filtrate was carried out by Fourier Transform Infrared spectrum (FTIR). High antimicrobial activities were observed by AgNPs at a low concentration of 0.01 ppm, however, no deleterious effect of AgNPs was observed on the development and occurrence of Drosophila melanogaster phenotype. The highest reduction in the viability of the human lung carcinoma and normal cells was attained at 0.2 AgNPs ppm.     

Resistive transition of the compound LaO0.89F0.11FeGe at 20 K

In this article, the synthesis and electrical resistivity measurement of LaO_0.89F_0.11FeGe are reported. The onset transition temperature was 20.6?K. Moreover, a clear anomaly was observed at 90?K in the ρ–T curve, which was much lower compared with the quaternary oxypnictides.     

Far-infrared probe of energy gap in LaO1−xFxFeGe compound

We report on the electrical resistivity and far-infrared reflectance measurements of LaO_1?xF_xFeGe samples. Furthermore, we introduce a new method to probe the energy gap and determine its value. The onset transition temperature was 22.8 K for x = 0.13, and a clear anomaly was observed at 90 K in the ρ(T) curve for x = 0.11 with T_c = 20.6 K. We clearly observed the phonon-suppressed feature in reflectance spectra where F-doping caused a strong suppression of a peak at 200 cm^?1. The energy gap above T_c, 2Δ = 2.10 meV, was determined from the measured spectra based on the changes in reflectivity by F-doping.