Acid-Catalysed Hydrolysis of Some Aromatic Cyclic Sulfamates

The acid catalysed hydrolysis of some cyclic sulfamates, X-3-(p-tolylsulfonyl)-1,2,3-benzoxathiazole 2,2-dioxides ( 1a , X = Me; 1b , X = H; 1c , X = Cl; 1d , X = NO 2 ) have been studied in concentrated aqueous sulfuric and perchloric acid solutions. Analysis of the data by the Excess Acidity Method, activation parameters, substituent, solvent deuterium isotope effect and order of the catalytic effects of the acids are all in agreement with an A-1 mechanism in the studied range.     

Dew Points of Binary Methane + Water: Measurement and Correlation

Experimental measurements of dew points for four methane + water mixtures between 2.6 2 10 5 Pa and 100.4 2 10 5 Pa and the temperature range from 225.5 K to 272.7 K were carried out. The experimental results were analysed in terms of both an equation of state model and an excess function-equation of state method, which reproduced the experimental data within AAD from 1.8 to 3.1 K and from 0.9 to 1.8 K, respectively.     

Density,viscosity and thermodynamic activation for viscous flow of water+sulfolane

Densities and viscosities for the system, water (W)?+?sulfolane (SFL), have been determined for the entire range of composition at temperatures ranging from 303.15 to 323.15?K. Density, excess molar volume, viscosity, excess viscosity and thermodynamic activation parameters for viscous flow have been calculated and plotted against the mole fraction of SFL. The measured properties and some of the derived properties have been fitted to appropriate polynomial equations. These have been explained in terms of such factors, as, dipole–dipole interaction, partial accommodation of water molecules into the structural network of SFL and H-bonding between SFL and H₂O.     

Volumetric behaviour of the (2,2,4-trimethylpentane + methylbenzene + butan-1-ol) ternary system and its binary sub-systems within the temperature range (298.15–328.15) K

Densities and speeds of sound of the (2,2,4-trimethylpentane + methylbenzene + butan-1-ol) ternary system as well as all its binary sub-systems were measured at four temperatures, namely 298.15 K, 308.15 K, 318.15 K, and 328.15 K at atmospheric pressure by a vibrating-tube densimeter DSA 5000. The binary (isooctane + toluene) system was studied previously. Excess quantities (molar volume, adiabatic compressibility, and isobaric thermal expansivity) of the mixtures studied were calculated from the experimental densities and speed of sounds. The excess molar volume data were correlated using the Redlich–Kister equation. Both the positive and S-shaped excess molar volume curves were found for the systems studied. The excess molar volumes versus concentration of binary systems differed in the shape and temperature dependence. The experimental binary data were compared with literature data. The experimental excess molar volumes were analyzed by means of the Extended Real Associated Solution (ERAS) model. The experimental data and the ERAS model can help to estimate real behaviour of the systems studied.     

Progress in the Understanding of the Key Pharmacophoric Features of the Antimalarial Drug Dihydroartemisinin: An Experimental and Theoretical Charge Density Study

The accurate, experimental charge density distribution, ρ( r ), of the potent antimalarial drug dihydroartemisinin (DHA) has been derived for the first time from single‐crystal X‐ray diffraction data at T=100(2) K. Gas‐phase and solid‐state DFT simulations have also been performed to provide a firm basis of comparison with experimental results. The quantum theory of atoms in molecules (QTAIM) has been employed to analyse the ρ( r ) scalar field, with the aim of classifying and quantifying the key real‐space elements responsible for the known pharmacophoric features of DHA. From the conformational perspective, the bicyclo[3.2.2]nonane system fixes the three‐dimensional arrangement of the 1,2,4‐trioxane bearing the active O? O redox centre. This is the most nucleophilic function in DHA and acts as an important CH???O acceptor. On the contrary, the rest of the molecular backbone is almost neutral, in accordance with the lipophilic character of the compound. Another remarkable feature is the C? O bond length alternation along the O‐C‐O‐C polyether chain, due to correlations between pairs of adjacent C? O bonds. These bonding features have been related with possible reactivity routes of the α‐ and β‐DHA epimers, namely 1) the base‐catalysed hemiacetal breakdown and 2) the peroxide reduction. As a general conclusion, the base‐driven proton transfer has significant non‐local effects on the whole polyether chain, whereas DHA reduction is thermodynamically favourable and invariably leads to a significant weakening (or even breaking) of the O? O bond. The influence of the hemiacetal stereochemistry on the electronic properties of the system has also been considered. Such findings are discussed in the context of the known chemical reactivity of this class of important antimalarial drugs.     

Calculations of Two and Three-Body Correlation Entropies at the Freezing Points of Soft-Core Fluids: Effect of the Softness on the Correlation Entropy

Two and three-body correlation entropies of model fluids, in which particles interact each other through the 4th, 6th, 9th and 12th-inverse-power potentials, were calculated from their atomic configurations obtained by molecular dynamics simulations at their freezing points. Besides the soft-core fluid model with the inverse-power potentials, hard-sphere and classical one-component plasma models were employed to provide a comparison with the entropies of the soft-core model. The correlation entropies were plotted as a function of the softness of the potential. These values were also compared with the excess entropies of the hard-sphere and the one-component plasma models at their freezing points.     

Statistical Spectral Analysis of liquid X-ray Diffraction Data

Abstract

The experimental procedure of determining the structure of a liquid by diffraction techniques is reformulated herein as a stochastic experiment subject to the data analysis formalism of statistical spectral analysis. Observed in such an experiment are averaged local microscopic fluctuations from the bulk density. The intensity function then represents a stochastic spectrum and it becomes necessary to statistically estimate a minimum bias, minimum variance covariance function which is the net radial distribution function. A low-pass tapered data window produces such an optimum estimate.     

Excess Molar Enthalpies for Isomeric Chlorobutanes with Isomeric Butanols

Abstract

Excess molar enthalpies for mixtures of each of the isomers of chlorobutane with each of the isomers of butanol were determined at the temperature 298.15 K and atmospheric pressure. Excess molar enthalpies are positive for all the mixtures. The results are discussed in terms of molecular interactions.     

Densities and viscosities of propylene carbonate with aromatic hydrocarbons (benzene, 1,4-dimethylbenzene and ethylbenzene) at 288.15, 298.15 and 308.15 K

Densities and viscosities of the binary mixtures of propylene carbonate with benzene, 1,4-dimethylbenzene and ethylbenzene were measured over the entire mole fraction range at 288.15, 298.15 and 308.15?K. Using the experimental values of densities and viscosities the excess molar volumes and viscosity deviations were calculated. The results were fitted by Redlich–Kister equation. The results were discussed in terms of intermolecular interactions.