Synthesis of reduced graphene oxide functionalized with methyl red dye and its role in enhancing photoactivity in TiO2–IL/WO3 composite for toluene degradation

Research on Chemical Intermediates - A nanostructured composite material was produced through sol–gel-assisted ionic liquid (IL) synthesized TiO2, WO3 and functionalized reduced graphene...     

Synthesis of azachromones and azachromanones

Chemistry of Heterocyclic Compounds - This minireview highlights known methods for the synthesis of azachromones and azachromanones, including the earliest and the latest examples of their...     

Highly Emissive Self‐Trapped Excitons in Fully Inorganic Zero‐Dimensional Tin Halides

The spatial localization of charge carriers to promote the formation of bound excitons and concomitantly enhance radiative recombination has long been a goal for luminescent semiconductors. Zero‐dimensional materials structurally impose carrier localization and result in the formation of localized Frenkel excitons. Now the fully inorganic, perovskite‐derived zero‐dimensional Sn^II material Cs₄SnBr₆ is presented that exhibits room‐temperature broad‐band photoluminescence centered at 540 nm with a quantum yield (QY) of 15±5 %. A series of analogous compositions following the general formula Cs_4?xA_xSn(Br_1?yI_y)₆ (A=Rb, K; x≤1, y≤1) can be prepared. The emission of these materials ranges from 500 nm to 620 nm with the possibility to compositionally tune the Stokes shift and the self‐trapped exciton emission bands.     

3-Fluoroalkyl (CF3, CHF2, CH2F) Cyclobutane-Derived Building Blocks for Medicinal Chemistry: Synthesis and Physicochemical Properties

Synthesis and physicochemical characterization of all possible cis- and trans-1,3-disubstituted cyclobutane-derived amines and carboxylic acids bearing mono-, di- and trifluoromethyl groups at the C-3 position is disclosed. Tetramethylammonium fluoride (TMAF)- or morpholinosulfur trifluoride (Morph-DAST)-mediated nucleophilic fluorination of appropriate cis- and trans-diastereomeric substrates was used as the key step for the preparation of CH₂F- and CHF₂-substituted derivatives. To obtain the corresponding cis- and trans-isomeric CF₃-substituted derivatives, resolution of known 3-(trifluoromethyl)cyclobutanecarboxylic acid (obtained as a mixture of diastereomers) was applied. The proposed procedures were suitable for the preparation of corresponding fluoroalkyl-substituted cyclobutane-derived amines and carboxylic acids on up to 50 g scale. All 12 building blocks obtained were characterized by measuring dissociation constants (pK_a) and lipophilicities (LogP, for model derivatives) to evaluate the effect of the fluoroalkyl substituents on their physicochemical properties relevant to further drug discovery applications.     

Quantification of local hydration at the surface of biomolecules using dual-fluorescence labels

By using four labels of the 3-hydroxyflavone family displaying selective sensitivity to hydrogen bond (HB) donors and poor response to other polar molecules, we developed an approach for measuring local water concentration [H(2)O](L) (or partial volume of water: W(A) = [H(2)O](L)/55.6) in the label surrounding both in solvent mixtures and in biomolecules by the intensity ratio of two emissive forms of the label, N*/T*. Using a series of binary water/solvent mixtures with limited preferential solvation effects, a linear dependence of log(N*/T*) on the local concentration of HB donor was obtained and then used as a calibration curve for estimating the W(A) values in the surroundings of the probes conjugated to biomolecules. By this approach, we estimated the hydration of the labels in different peptides and their complexes with DNAs. We found that W(A) values for the label at the peptide N-terminus are lower (0.63-0.91) than for free labels and depend strongly on the nature of the N-terminal amino acid. When complexed with different DNAs, the estimated hydration of the labels conjugated to the labeled peptides was much lower (W(A) = 0-0.47) and depended on the DNA nature and linker-label structure. Thus, the elaborated method allows a site-specific evaluation of hydration at the surface of a biomolecule through the determination of the partial volume of water. We believe the developed procedure can be successfully applied for monitoring hydration at the surface of any biomolecule or nanostructure.     

Mechanism of atmospheric CO2 fixation in the cavities of a dinuclear cryptate

Using density functional theory (DFT) methods, we have investigated two possible mechanisms for atmospheric CO(2) fixation in the cavity of the dinuclear zinc(II) octa-azacryptate, and the subsequent reaction with methanol whereby this latter reaction transforms the (essentially) chemically inert CO(2) into useful products. The first mechanism (I) was proposed by Chen et al. [Chem.-Asian J. 2007, 2, 710], and involves the attachment of one CO(2) molecule onto the hydroxyl-cryptate form, resulting in the formation of a bicarbonate-cryptate species and subsequent reaction with one methanol molecule. In addition, we suggest another mechanism that is initiated via the attachment of a methanol molecule onto one of the Zn-centers, yielding a methoxy-cryptate species. The product is used to activate a CO(2) molecule and generate a methoxycarbonate-cryptate. The energy profiles of both mechanisms were determined, and we conclude that, while both mechanisms are energetically feasible, free energy profiles suggest that the scheme proposed by Chen et al. is most likely.     

On some integral-consistent methods for calculating magnetohydrodynamic phenomena in problems of computational astrophysics

When constructing difference schemes for calculating complex problems of computational astrophysics considering magnetohydrodynamic and gravitational phenomena, the processes of matter overcompression (with a change in density by several orders of magnitude) should be taken into account, and it is important at a discrete level to take into account the corresponding energy transformations of magnetohydrodynamic, gravitational, kinetic, and internal energy during the evolution of a star. This problem is solved by constructing completely conservative difference schemes in a view of these magnetohydrodynamic processes and self-gravitating phenomena. In this work, to study and apply the difference methods for solving problems of magnetic gas dynamics, a discrete representation of symmetrized spatial deformations of the medium was obtained. The representation is consistent with changes in the magnetic, kinetic, and internal energies and does not lead to their distortions when the matter is overcompressed.     

Nonlinear vibration analysis of isotropic cantilever plate with viscoelastic laminate

The nonlinear vibration of an isotropic cantilever plate with viscoelastic laminate is investigated in this article. Based on the Von Karman’s nonlinear geometry and using the methods of multiple scales and finite difference, the dimensionless nonlinear equations of motion are analyzed and solved. The solvability condition of nonlinear equations is obtained by eliminating secular terms and, finally, nonlinear natural frequencies and mode-shapes are obtained. Knowing that the linear vibration of this type of plate does not have exact solution, Ritz method is employed to obtain semi-analytical nonlinear mode-shapes of transverse vibration of this plate. Airy stress function and Galerkin method are employed to reduce nonlinear PDEs into an ODE of duffing type. Stability of plate and chaotic behavior are investigated by Runge–Kutta method. Poincare section diagrams are in good agreement with results of Lyapunov criteria.     

Numerical study of the effect of secondary electron emission on the sheath characteristics in q-non-extensive plasma

In this paper, a plasma sheath containing primary electrons, cold positive ions, and secondary electrons is studied using a one-dimensional fluid model in which the primary electrons are described by q-non-extensive distribution according to the Tsallis statistics. Based on the Sagdeev potential method and the current balance relation, a modified sheath criterion, and floating potential are established theoretically. The effect of secondary electron emission on q-non-extensive plasma sheath characteristics have been numerically examined. A significant change is observed in the quantities characterizing the non-extensive plasma sheath with the presence of the secondary electrons. It is found that the sheath properties with super-extensive distribution and sub-extensive distribution are different compared with plasma sheath with Maxwell distribution .