The Products of Suzuki Reaction of Ethyl 4-Chloro-5-Methylthieno[2,3-d]Pyrimidine-6-Carboxylate with Potassium Allyltrifluoroborate and Transformations Thereof

Chemistry of Heterocyclic Compounds - 5-Methylthieno[2,3-d]pyrimidine-6-carboxylates substituted with prop-1-en-1-yl and hexa-1,5-dien-3-yl fragments in the C-4 position of the heterocycle were...     

Bioactive constituents of Iris hybrida (Iridaceae): Processing effect

Iris genus plants are a valuable source of bioactive compounds, which are an important component for pharmaceutical development. The present article shows the potential for mineral nutrition with application of magnesium sulfate, iron chelates and potassium oxide affecting the phenolic compound contents in Iris hybrida ‘Tsikavynka’, I. hybrida ‘Tambo’ and I. hybridа ‘Widecombe Fire’. The effect of mineral processing was specific to plant organs and varied in the component composition. The Iris rhizomes had an increased total phenolic compound content after treatment (up to 10% of the total isoflavonoid content, up to 8% of phenolic acids, up to 5% of γ-pyrones and up to 13% of flavonoids), determined using UV–vis spectroscopy. A positive effect of nutrition on the biosynthesis and content of individual isoflavonoids (tectoridin, nigricin d -glucoside, genistin, iristectorigenin B, nigricin, irigenin and irisolidone) and xanthone mangiferin in Iris rhizomes by HPLC was established. In addition, an increase in the chlorogenic acid amount in Iris leaves was noted. The results demonstrate the sensitivity of Iris phenylpropanoid metabolism to mineral nutrition and can be used to predict medical plant cultivation with increased content of bioactive constituents.     

Stabilization of polystyrene by styrylquinoline containing methacrylates

Abstract

The thermostability of polysterene with/without new styrylquinoline containing methacrylic fragments has been described in the present work. Polystyrene and copolymers based on styrene and new methacrylic styrylquinoline containing monomers were synthesized by free radical thermoinitiated polymerization in the presence of 2,2′-azobisisobutyronitrile (1?wt%) as initiator at inert atmosphere. The impact of 2-[2-(4-methoxyphenyl)ethenyl]quinolin-8-yl 2-methylpropyl-2-enoate (М1), 2-(2-phenylethenyl)quinolin-8-yl 2-methylpropyl-2-enoate (М2), 2-[2-(4-nitrophenyl)ethenyl]quinolin-8-yl 2-methylpropyl-2-enoate (М3) on thermal stability of polystyrene was investigated. The thermostability of polystyrene and copolymers ST:M1, ST:M2, ST:M3 were studied by dynamic thermograviametric analysis. It was shown that destruction of polystyrene with corresponding units M1-M2 starts at 41–42°С higher, than reference polystyrene.     

Phase field modeling precipitation of β-phase and mechanical properties change in Zr–Nb alloys under neutron irradiation

ABSTRACT

We study microstructure transformation in Zr–Nb system under neutron irradiation and its mechanical properties change under mechanical loads in a form of shear deformation by using phase field methodology. The developed phase field approach takes into account defects dynamics based on reaction rate theory and elastic contribution to study mechanical properties change. A numerical modeling is provided in three stages: sample preparation, irradiation of the prepared sample and mechanical loading of the irradiated sample. A precipitation of β-Niobium particles of the size of several nanometers is discussed. Results of phase field modeling indicate that β-Niobium particles grow slowly during irradiation due to point defects rearrangement. Statistical analysis of dynamics of radiation-induced microstructure transformations is provided. Simulation results of shear deformation of pre-irradiated and post-irradiated alloys are discussed. Maps of local distribution of strain and stress and strain–stress curves are obtained. Results are verified with experimental data.     

Synthesis of 4-polyfluoroalkyl-1,3-dithiolanes via [3+2] cycloaddition of thiocarbonyl ylide to polyfluoroalkanethioamides

Chemistry of Heterocyclic Compounds - New 4-polyfluoroalkyl-1,3-dithiolanes were synthesized by reaction of polyfluoroalkanethioamides with thiocarbonyl ylide that was generated in situ by...     

Effect of wastes formed in processing of vegetable raw materials on the corrosion of steel in corrosive media

Effect of liquid and dry extracts of rice, buckwheat, and sunflower husks on the corrosion of St.3 steel in water-salt and acid media was studied by gravimetric and potentiodynamic methods. The action of the extracts on the surface morphology of St.3 steel samples was examined by electron microscopy and electron microprobe analysis.     

Computational study of the aminolysis of anhydrides: effect of the catalysis to the reaction of succinic anhydride with methylamine in gas phase and nonpolar solution

Different possible pathways of the aminolysis reaction of succinic anhydride were investigated by applying high level electronic structure theory, examining the general base catalysis by amine and the general acid catalysis by acetic acid, and studying the effect of solvent. The density functional theory at the B3LYP/6-31G(d) and B3LYP/6-311++G(d,p) levels was employed to investigate the reaction pathways for the aminolysis reaction between succinic anhydride and methylamine. The single point ab initio calculations were based on the second-order M?ller-Plesset perturbation theory (MP2) with 6-31G(d) and 6-311++G(d,p) basis sets and CCSD(T)/6-31G(d) level calculations for geometries optimized at the B3LYP/6-311++G(d,p) level of theory. A detailed analysis of the atomic movements during the process of concerted aminolysis was further obtained by intrinsic reaction coordinate calculations. Solvent effects were assessed by the polarized continuum model method. The results show that the concerted mechanism of noncatalyzed aminolysis has distinctly lower activation energy compared with the addition/elimination stepwise mechanism. In the case of the process catalyzed by a second methylamine molecule, asynchronous proton transfer takes place, while the transition vectors of the acid-catalyzed transition states correspond to the simultaneous motion of protons. The most favorable pathway of the reaction was found through the bifunctional acid catalyzed stepwise mechanism that involves formation of eight-membered rings in the transition state structures. The difference between the activation barriers for the two mechanisms averages 2 kcal/mol at various levels of theory.     

Single nanoparticle plasmonic devices by the "grafting to" method

Hierarchically organized single-nanoparticle structures synthesized in this work consisted of a 200 nm silica core and a pH-responsive poly(2-vinylpyridine) shell decorated with 15 nm gold nanoparticles. pH changes in the range of 3-6 back and forth results in a swelling-shrinking polymer brush shell and, thus, in the tuning distance between noble nanoparticles. A change in the interparticle distance is accompanied by a very pronounced shift in the maximum wavelength of the surface plasmon absorption peak. The dispersion of the resulting composite nanoparticles reversibly changed color from red to purple-blue as the pH changed from 2.5 to 6. Such hierarchically assembled nanostructures can be used as free-standing single-particle sensors in various miniaturized analytical systems.     

Biochemically controlled bioelectrocatalytic interface

A switchable bioelectrocatalytic system for glucose oxidation controlled by external biochemical signals exemplifies interfacing between bioelectronic and biochemical ensembles.     

Analytical expressions for partial wave two-body Coulomb transition matrices at ground-state energy

Leaning upon the Fock method of the stereographic projection of the three-dimensional momentum space onto the four-dimensional unit sphere the possibility of the analytical solving of the Lippmann–Schwinger integral equation for the partial wave two-body Coulomb transition matrix at the ground bound state energy has been studied. In this case new expressions for the partial p$p$-, d$d$- and f$f$-wave two-body Coulomb transition matrices have been obtained in the simple analytical form. The developed approach can also be extended to determine analytically the partial wave Coulomb transition matrices at the energies of excited bound states.