Structural conformation in a poly(ethylene oxide) film determined by X-ray emission spectroscopy

The electronic structure of pol(ethylene oxide) (PEO) in a thin (<1 mu) film sample was experimentally probed by X-ray emission spectroscopy. Both nonresonant and resonant X-ray emission spectra were simulated by using density functional theory (DFT) applied to four different models representing different conformations in the polymer. Calculated spectra were compared with experimental results for the PEO film. It was found that the best fit was obtained with the polymer conformation in PEO electrolytes from which the salt (LiMF6, M = P, As, or Sb) had been removed. This conformation is different from the crystalline bulk polymer and implies that film casting, commonly used to form electrolytes for Li polymer batteries, induces the same conformation in the polymer not depending upon the presence of salt.     

Thermodynamic estimate of the minimal energy and useful work of separation during impurity concentration and deep purification of substances in an ideal cascade

Thermodynamic analysis of a separation process occurring at constant temperature T and pressure p is carried out using the model of an ideal cascade consisting of two equivalent sections and a number of stages of equilibrium (quasi-static) separation of components of an ideal gaseous solution. The useful work of separation and the lowest energy required for concentrating impurities and deep purification of substances in an ideal cascade are estimated.     

A challenging synthesis of new 1,3,4‐thiadiazole derivatives starting from 2‐acylamino‐3,3‐dichloroacrylonitriles

Available 2‐acylamino‐3,3‐dichloroacrylonitriles, when treated with hydrazine hydrate, provide 2‐alkyl‐ or 2‐aryl‐5‐hydrazino‐1,3‐oxazole‐4‐carbonitriles that readily add alkyl or aryl isothiocyanates and the adducts formed recyclize on heating. Finally, the synthesis results in 5‐alkyl(aryl)amino‐1,3,4‐thiadiazol‐2‐yl(acylamino)acetonitriles or the products of their further cyclization, 2‐(5‐amino‐1,3‐ oxazol‐2‐yl)‐1,3,4‐thiadiazole derivatives. The structures of the novel substituted 1,3,4‐thiadiazoles are corroborated spectroscopically as well as by X‐ray diffraction method. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:454–458, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20041     

Influence of Environmental Parameters on the Stability of the DNA Molecule

Fluctuations in viscosity within the cell nucleus have wide limits. When a DNA molecule passes from the region of high viscosity values to the region of low values, open states, denaturation bubbles, and unweaving of DNA strands can occur. Stabilization of the molecule is provided by energy dissipation—dissipation due to interaction with the environment. Separate sections of a DNA molecule in a twisted state can experience supercoiling stress, which, among other things, is due to complex entropic effects caused by interaction with a solvent. In this work, based on the numerical solution of a mechanical mathematical model for the interferon alpha 17 gene and a fragment of the Drosophila gene, an analysis of the external environment viscosity influence on the dynamics of the DNA molecule and its stability was carried out. It has been shown that an increase in viscosity leads to a rapid stabilization of the angular vibrations of nitrogenous bases, while a decrease in viscosity changes the dynamics of DNA: the rate of change in the angular deviations of nitrogenous bases increases and the angular deformations of the DNA strands increase at each moment of time. These processes lead to DNA instability, which increases with time. Thus, the paper considers the influence of the external environment viscosity on the dissipation of the DNA nitrogenous bases’ vibrational motion energy. Additionally, the study on the basis of the described model of the molecular dynamics of physiological processes at different indicators of the rheological behavior of nucleoplasm will allow a deeper understanding of the processes of nonequilibrium physics of an active substance in a living cell to be obtained.     

Strain mapping analysis of textile composites

The focus of the work is meso-scale analysis (scale level of the fabric unit cell) of textile composite deformation and failure. The surface strain measurement is used for: (1) experimental investigation, which includes study of strain distribution at various stages of deformation, plasticity detection, damage initiation; (2) numerical validation of the correspondent finite element (FE) models. Two examples are considered: carbon-epoxy triaxial-braided and glass polypropylene-woven composite. The surface strain measurement (by digital image correlation technique) accompanies the tensile tests, aiming at: (1) elastic anisotropic constants characterisation, (2) study of non-linear material behaviour (for the thermoplastic composite), (3) control of homogeneity of the macro-strain distribution, and (4) analysis of damage initiation in brittle composites. Validation of meso-FE models by strain measurements encounters difficulties arising from (1) resolution of the strain measurements, (2) irregularities of the initial structure such as random layer nesting, ply interaction, and deviation of yarns from their theoretical position, which affects the measured strain fields. The paper discusses these difficulties and demonstrates a qualitative agreement with the FE analysis of idealised composite configurations.     

Total synthesis and structural elucidation of azaspiracid-1. Synthesis-based analysis of originally proposed structures and indication of their non-identity to the natural product

The key building blocks (6, 7, and 8) for the intended construction of the originally proposed structures of azaspiracid-1, a potent marine-derived neurotoxin, were coupled and the products elaborated to the targeted compounds (1a,b) and their C-20 epimers (2 and 3). The assembly of the three intermediates was accomplished by a dithiane-based coupling reaction that united the C(1)-C(20) (7) and C(21)-C(27) (8) fragments, followed by a Stille-type coupling which allowed the incorporation of the C(28)-C(40) fragment (6) into the growing substrate. Neither of the final products (1a,b) matched the natural substance by TLC or (1)H NMR spectroscopic analysis, suggesting one or more errors in the originally proposed structure for this notorious biotoxin.     

Bifurcation analysis of a two-DoF mechanical system subject to digital position control. Part II. Effects of asymmetry and transition to chaos

Considering a two DoF system subject to digital position control, of interest for robotic application, we analyze the dynamics of the system at the intersection of two loci of Neimark–Sacker bifurcations, where a double Neimark–Sacker bifurcation is taking place. In the system, the saturation of the control force is the only nonlinear term considered, other than this, the system is piecewise linear. Starting from the analytical investigation already performed in Part I (Habib et al. in Nonlin. Dyn., under review, 2013), in this paper the effects of an asymmetry of the saturation of the control force are investigated, both analytically and numerically. The results show the increasing complexity of the dynamics for a more and more asymmetric system. First, the asymmetry is making the bifurcation transit from supercritical to subcritical, then it generates a stable torus that breaks down into a strange attractor, associated with a chaotic motion. In the last part of the paper, the torus breakdown and the onset of chaos are investigated, furthermore the evolution of complex dynamics through regions of phase locking and higher-dimensional chaos is outlined.     

In Vitro Activity of Organochalcogen Compounds: I. Cytotoxic Effect of 4-(1,2,3-Thiadiazol-4-yl)furans Against K562 and HeLa Tumor Cell Lines

Russian Journal of General Chemistry - In vitro antitumor activity of some 4-(1,2,3-thiadiazol-4-yl)furans was studied against erythroleukemia (K562) and cervical carcinoma (HeLa) cell lines.     

Out-cage metal ion coordination by novel benzoazacrown bisamides with carboxyl,pyridyl and picolinate pendant arms

A new series of macrocyclic diamides with carboxyl, pyridyl and picolinate pendant arms have been synthesized and the stability constants of their complexes with Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺ in water were determined. Complexes with a stoichiometry of 1 : 1 (M: L) were found for all ligands with the exception of 15-membered crown ethers with one pendant carboxyl or pyridine group. The ligand containing two picolinate backbone groups exhibits the highest values of the stability constants for all studied cations (logβ_ML?=?12.5–15.7). X-ray study of free ligands showed that the introduction of benzene and amide fragments into the macrocyclic moiety provides a flatten open structure of the ligand. The crystallographic analysis of Cu²⁺ and Zn²⁺ complexes revealed the external coordination of the metal atom by amine N atoms of the macrocycle and heteroatoms of the pendant groups.