Study of oriented polyethylene structures using a Raman longwave acoustic mode

This paper concerns the basics of using longwave (low-frequency) Raman spectroscopy in the region of a longitudinal acoustic mode for the study of structural features of polymers. Using ultrahighmolecular- weight polyethylene (UHMW PE)-based reactor powders, gels, and oriented fibers obtained by the gel technology, the length distribution of straight-chain segments and its relation to the morphology of the sample were analyzed. An important role of the low-frequency Raman spectroscopy in creating domestic gel technology for preparing ultrahigh-strength threads from polyethylene was demonstrated.     

Structural properties of star-shaped polyions: Entropic sampling

The method of entropic sampling within the Wang–Landau algorithm (a modern variant of the Monte Carlo method) is used to determine the densities of energy states of a strongly charged star-shaped polyelectrolyte within the framework of the lattice model. The equilibrium thermal and structural properties of the polyelectrolyte with the number of arms f ≤ 6 and the length of arms N _arm ≤ 73 in a wide temperature range are determined from the density of states. Such characteristics as the free energy, the mean-squared radius of gyration, its components, and the parameters characterizing the shape of a polyion are calculated. It is found that the concentration, length, and number of arms affect the thermal and structural properties. The main attention is focused on the effect of temperature on these properties. The coil-to-globule transition is detected, while for the polyion with the highest length of arms (N _arm = 24) the transition from the liquid globule to the crystal-like one is observed. Differences in the properties of the star-shaped and corresponding linear polyions are characterized.     

Uncatalyzed synthesis of new substituted dihydro-2H-dipyrimido[1,2-a,4,5-d]pyrimidine-2,4(3H)-dione

Research on Chemical Intermediates - A convenient and new method has been developed for the synthesis of highly substituted dihydro-2H-dipyrimido[1,2-a,4,5-d]pyrimidine-2,4(3H)-dione derivatives by...     

New polymer composites based on keratin and polyethylene

New biodegradable composites based on keratin and polyethylene have been produced under shear deformation. It has been demonstrated that the introduction of keratin leads to an increase in elastic modulus and to a decrease in ultimate tensile strength and elongation at break of the compositions. Elongation at break ε_b depends on the keratin dispersity; the highest ε_b values are observed for the compositions containing the smallest keratin particles. It has been shown that the compositions are susceptible to mold fungi; i.e., they are biodegradable.     

Drying of colloidal solutions of fluoroalkyl oligomers

The change in the supramolecular structure upon drying (solvent removal) of colloidal solutions of fluoroalkyl oligomers at atmospheric pressure has been studied using atomic force microscopy. In an initial colloidal solution, micrometer-sized particles of the dense phase consist of randomly oriented oligomers in the form of rigid rods of a 3–5 nm length forming a porous framework filled with solvent molecules, which solvate the oligomer chains. The drying-induced capillary pressure, which in nanosized pores is of the same order of magnitude as the solvation energy, leads to framework deformation, collapse of the pores, and the formation of lamellar and dendritic structures on a 50–100 nm scale. The ordering of these structures (formation of blocks of parallel oriented fibers typical of a fluoroplastic) increases as the heat-treatment temperature and the drying rate are increased, increasing the roughness of the surface (ratio of real to smooth surface area) and its hydrophobicity.     

Visualization of supramolecular framework of perfluorinated-oligomer colloid particles by supercritical drying

Aerogels of the tetrafluoroethylene radical polymerization products H(C₂F₄)_nR, where R is the radical formed by the abstraction of a hydrogen atom from a solvent molecule, have been obtained by replacing the solvent with supercritical CO₂ and its subsequent rapid evaporation. According to the data of scanning electron and atomic force microscopy, the aerogel consists of loosely bound particles of 1–3 μm in diameter, which is two to three times that of colloid particles in the initial solution, where the particles consist of an oligomer framework filled with solvent molecules. The internal structure of the framework is manifested in the surface topography with a roughness coefficient of 1.6–1.8. High roughness leads to the formation of ultrahydrophobic coatings with contact angles of >160°. A model of supercritical drying in which the solvent is removed from the colloidal particles without alteration of the supramolecular structure is discussed.     

Formation of benzenediols upon electron-beam distillation of lignin mixtures with alkanes

In the process of the electron-beam distillation of lignin, its conversion into benzenediols increases in the presence of alkanes in the irradiated sample. An increase in the yield of benzenediols is accompanied by a decrease in the fractions of guaiacol, creosol, ethylguaiacol, and vinylguaiacol in the tar distilled off. It has been noted that alkanes serve as an additional source of atomic hydrogen and alkyl radicals, which, in turn, play a key role in the formation of benzenediols. In the presence of alkanes in the irradiated sample, guaiacol can be the main precursor of catechols; the proportion of guaiacol in the tar is almost three times below that in the case of distillation of individual lignin. It has been hypothesized that the chain decomposition of lignin can occur with the participation of ?H and ?CH₃ radicals.     

The relationship between self-organization and membrane effects of aqueous dispersion systems of the thyroliberin oligopeptide

The relationship between rearrangement of the dispersed phase inducing considerable changes in the pH and nonmonotonic concentration dependences of membrane effects in aqueous systems of the endogenous regulatory peptide, thyroliberin (thyrotropin-releasing hormone), in 10^–3–10^–16 mol/L concentration range was demonstrated for the first time. The membrane structure modification in the 10^–13–10^–16 mol/L range was found to be due to accumulation of nanoassociates, while the oppositely directed pronounced structural changes in the 10^–6–10^–12 mol/L range may be associated with the coexistence and rearrangement of dispersed phases of various nature (domains and associates) whose action on membrane lipid components is regulated in this concentration range by the correlated changes in the dispersed phase parameters and pH.     

Study on the equilibria of the complex formation of molybdenum(VI) with 3,5-dinitrocatehol and 3-(2-naphthyl)-2,5-diphenyl-2H-tetrazolium chloride

The formation of an ion-associated complex between the anionic chelate of Mo(VI)–3,5-dinitrocatehol (3,5-DNC) and the cation of 3-(2-naphthyl)-2,5-diphenyl-2H-tetrazolium chloride (TV) in the liquid–liquid extraction system Mo(VI)–3,5-DNC–TV–H₂O–CHCl₃ was studied by spectrophotometry. The optimum conditions for the complex formation and extraction of the ion-associated complex were established. The effect of co-existing ions and reagents on the process of complex formation was investigated under optimum extraction conditions. The validity of Beer’s law was checked and some analytical characteristics were calculated. The association process in aqueous phase and the extraction equilibria were investigated and quantitatively characterized. The following key constants of the processes were calculated: association constant, distribution constant, extraction constant and recovery factor. The molar ratio of the reagents was determined by independent methods. Based on this, a reaction scheme, a general formula and a structure of the complex were suggested.     

Electronic properties of achiral and chiral gold nanotubes

The band structure of ten single-walled gold nanotubes of different radius and chirality angle have been calculated by the linearized augmented cylindrical wave method. For all tubes, the Fermi level crosses the half-filled band; therefore, the tubes are characterized by a metallic electronic structure. The band structure of the nanotubes changes relatively weakly with a change in nanotube structure. The valence band width for all the tubes is 9.1 eV. The density of states at the Fermi level remains unaltered with a change in chirality angle and decreases by 30% with an increase in radius from 3 to 12 Å.